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Mechanistic and site isolation studies of transition metal oxidation catalysts

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Mechanistic and site isolation studies of transition metal oxidation catalysts
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Pribich, David Chappel, 1957-
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English
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vii, 145 leaves : ill. ; 28 cm.

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Catalysts ( jstor )
Chlorides ( jstor )
Ethanol ( jstor )
Gels ( jstor )
Ions ( jstor )
Ligands ( jstor )
Oxidation ( jstor )
Rhodium ( jstor )
Silica gel ( jstor )
Solvents ( jstor )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Transition metal catalysts ( lcsh )
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bibliography ( marcgt )
non-fiction ( marcgt )

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Thesis:
Thesis (Ph. D.)--University of Florida, 1985.
Bibliography:
Bibliography: leaves 139-144.
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by David Chappel Pribich.

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MECHANISTIC AND SITE ISOLATION STUDIES
OF TRANSITION METAL OXIDATION CATALYSTS
By
DAVID CHAPPEL PRIBICH
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN
PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1985


To Susan, Jean, Mitch and Pat Pribich


TABLE OF CONTENTS
ABSTRACT
CHAPTER
I GENERAL INTRODUCTION
II THE SPECIFIC OXIDATION OF [Rh(CO),
0, VIA THE COORDINATION OF IN SITO
HYDROGEN PEROXIDE
Introduction
Background
Results and Discussion
Characterization of the Catalyst
as a Rhodium(III) Chloride Complex . .
Mechanism of the 0~ Oxidation of
[Rh(CO)_C1]- to Rhodium(III)
Chloride
Conclusion
Experimental Section
Catalytic Oxidation of 1-Hexene
Preparation of RhCl, (H-,0) 2CH,-
CH OH (II)
Determination of Acetone Production. . .
Titration of [Rh(CO)-Cl], with
HOOH .
IllENHANCED SITE ISOLATION ON SILICA GEL AND
IMPROVED LIFETIMES OF SITE ISOLATED CATALYSTS .
Introduction
Results and Discussion
Polymer Support of the Catalyst
Catalytic Oxidations of 1-Hexene by
Supported Complexes
Alkyl Covering of the Silica
Surface to Improve Site Isolation
and Catalysis
Catalytic Oxidations Using Alkylated
Silica Gels as Solid Supports
Possible Effects of a Different
Rhodium Catalyst Characterization . .
Conclusions
Cl ] 2 BY
GENERATED


Experimental 86
General Procedures 86
Preparation of Silica Gel Supports .... 86
Determination of -SH on Silica Gel .... 87
Catalytic Oxidations of 1-Hexene 89
IV THE SYNTHESIS AND CATALYTIC APPLICATIONS OF A
MULTIDENTATE LIGAND AND CORRESPONDING METAL
COMPLEXES BOUND TO SILICA GEL 90
Introduction 91
Results and Discussion 94
Synthesis of a Salen Ligand on
Silica Gel 94
Oxygen Transfer Using [SG ]-Fe(III)-
SalDPT and [SG ]-Mn (11) Sal DPT 101
Synthesis of [SG ]-Fe(II)SalDPT 107
Incorporation of an Active Metal
into a Functionalized Support 110
Synthesis of a Silica Gel Anion
Exchange Resin 117
Titanium Carmde as a Solid
Support 118
Fenton Chemistry 127
Experimental 128
Silica Gel 128
Functionalization of Silica Gel
with l-tnmethoxysilyl-2-( p,m,-
chloromethylphenylethane) 129
Preparation of Silica Gel Bound
3,3 '-Immodipropionitnle 129
Preparation of Silica Gel Bound
bis-(3-aminopropy1)amine [SGj-DPT .... 130
Condensation of Salicylaldehyde with
[SG]-DPT 131
Incorporation of Metal Ions into
[SG ]-SalDPT 132
Incorporation of Fe(II) into [ SG]-
SalDPT 132
Incorporation of Cu(II) into the
Silica Gel Matrix 133
Preparation of Silica Gel Anion
Exchange Resins 134
Titanium Carbide as a Solid
Support 133
Fenton Chemistry 137
V GENERAL CONCLUSION 138
REFERENCES 139
BIOGRAPHICAL SKETCH 145
iv


Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
MECHANISTIC AND SITE ISOLATION STUDIES
OF TRANSITION METAL OXIDATION CATALYSTS
By
David Chappel Pribich
May, 1985
Chairman: Russell S. Drago
Major Department: Chemistry
Mechanistic work reported here involves the investi
gation of the oxidation of 1-hexene to 2-hexanone catalyzed
by Rh(III)/Cu(II) mixtures. A number of results are obtained
that indicate that [RhtCO^Cl^ as a catalyst precursor must
be converted to a rhodium(III) complex before catalysis
occurs. The oxidation of the rhodium(I) precursor to the
active rhodium(III) catalyst in the absence of copper is
reported in detail. An unusual mechanism results which
involves the in situ production of hydrogen peroxide from the
alcohol solvent reduction of 0^. The hydrogen peroxide then
oxidizes [Rh(CO)2ClJ2 to an unstable [Rh(CO)(00H)(?)]
v


intermediate. This oxidation occurs only in solvents
capable of reducing 0-, .
Cofunctionalization of silica gel with trialkylchloro-
silanes and (CH^O)^SiCH^CH^CH^SRh(CO)^ produces a catalyst
for the oxidation of 1-hexene that can be compared with a
catalyst that does not have an R^Si- covering. Physical
methods are used to determine the concentration of groups on
the silica surface and also to determine the loading at
which site separation occurs. The alkylated supports can be
loaded with a greater concentration of the site-isolated
rhodium complex producing catalysts which have greater
activity per gram of catalyst and longer lifetimes than the
corresponding catalysts produced with non-alkylated silica
gels. Increasing the length of the alkyl group used to cover
the surface decreases the effectiveness of the silica as a
catalytic support and eventually leads to a catalyst surface
that is not wetted by ethanol solvent.
A three nitrogen, two oxygen salen-type ligand was
successfully synthesized on silica gel. Cobalt, copper,
manganese and iron metal ions were incorporated into the
supported ligand system. The iron(III) and manganese(11)
systems achieved oxygen atom transfer from iodosylbenzene to
a cyclohexene substrate producing different product ratios
than homogeneous tetraphenylporphyrinato metal systems have
yielded and are also the first supported systems to
achieve this process.
vi


Several other results are reported, including the
preparation of an air sensitive iron(II) silica gel bound
complex, incorporation of copper into the silica gel matrix,
preparation of a silica gel based anion exchange resin, and
examination of titanium carbide as a catalytic support.
Vll


CHAPTER I
GENERAL INTRODUCTION
The efficient conversion of ubiquitous substances on
this planet into other useful species is a desirable and
perhaps even honorable goal which correspondingly attracts
the efforts of large segments of the scientific community.
Specifically, a subset of this broad area is the efficient
catalytic use of naturally occurring dioxygen via interaction
with transition metal centers. The following chapters will
describe investigations which in some way involve this area
of research. A rather detailed study on the formation and
nature of a specific homogeneous rhodium oxidation catalyst
is presented in the second chapter.
The general interest in the Chapter II catalyst led to
work which supported the catalytic system on an inorganic
polymeric solid. Subsequent efforts to maximize the
efficiency of this supported system while gaining detailed
information on the support medium itself are represented in
the third chapter.
1


2
A general broadening of study to include different
metals, ligands, substrates and even solid supports led to
further research; the various results of which are detailed
in the fourth chapter.
Specific background information and introduction is
included with each topic as it is discussed. The general
introduction provided by this brief overview should then
allow comprehension of the pattern of research on
interrelated topics presented in the following.


CHAPTER II
THE SPECIFIC OXIDATION OF [Rh(CO)-Cl],
BY 0- VIA THE COORDINATION OF IN 'SITU2
GENERATED HYDROGEN PEROXIDE
Introduction
Homogeneous catalysis has developed rapidly during the
last twenty years as organometallic chemistry has been firmly
established as a major discipline within inorganic chemistry.
The search for new and more efficient catalysts was
intensified as the finite nature of the crude oil supplies
which provide the feedstocks of many important chemical
processes was more closely realized. Oxidations have
specifically received much attention; there have been
estimates that an oxidation step is involved in the
production of over 50% of the chemicals manufactured
industrially. * Water, alky lperoxides and dioxygen are
frequently used as oxidation reagents. Dioxygen is the most
desirable one, not only due to its obvious availability, but
also because of its favorable energetics.
3


4
Homolytic and heterolytic are the two major categories
into which metal catalyzed homogeneous oxidations have most
2 3
often been divided. Homolytic oxidations are those in
which radical intermediates are produced during the oxidation
process. However, the drawback of most radical processes is
a lack of product selectivity, and that is also a major
problem in these oxidations. One reason for this lack of
specificity is that in many homogeneous metal catalyzed
oxidations of hydrocarbon by 0^ the metals are involved in
4-9
just the first step of reaction. These metals decompose
peroxides and thus initiate free-radical autoxidations.
These free radicals then react with substrates such as
olefins leading to the formation of several products.
Heterolytic oxidations, also known as nonfree-radical
oxidations, involve binding of a substrate to a metal center,
rearrangement, and later release of products. The Pd/Cu
catalyzed oxidation of ethylene to acetaldehyde in the
presence of water^ (the Wacker process) is one well-studied
example. The systems which undergo this type of oxidation
have been the focus of much research aimed at adjusting the
metal centers in order to improve catalytic activity. This
has been especially true since the discovery of Vaska's
complex, Ir(P(CgH^)^)2(CO)Cl, and the realization that it is
able to reversibly bind dioxygen.^ This "oxygen-atom
transfer process" does not involve free radicals and results
in product specificity. Since Vaska's complex was discovered
several 0^ oxidations of non-organic substrates have been


5
12-19
judged to occur by the O-atom transfer process. General
knowledge of this type of reaction is largely dependent upon
the ability to procure detailed mechanistic information. A
mechanistic investigation of one reaction will be presented
in the following sections.
Background
Considering specifically rhodium catalyzed oxidations
of hydrocarbons by dioxygen, several examples have been
reported which seemingly do not proceed by either free
2 o 2 4
radical or simple Wacker processes. One of these is
the rhodium/copper co-catalyzed oxidation of terminal olefins
20
to 2-ketones with >98% specificity (reaction 1).
2CH2=CHR + 02 2CH 3C(O)R (1)
The Wacker-Smidt process refers to the palladium(II)/-
copper(II) co-catalyzed oxidation of olefins to ketones and
2 s_2 6
aldehydes using water as the direct oxidant.
Palladium(O) is produced as an intermediate in this process,
and the copper(II) is necessary to oxidize it back to Pd(II),
the active catalyst. Only a stoichiometric reaction occurs
and Pd(0) metal is produced if no Cu(II) is used. The
general steps of the mechanism and the net reaction are shown


6
below (reactions 2-5) for the catalytic oxidation of ethylene
to acetaldehyde.
Pd(II) + H20 +
ch2=ch2
+ Pd(0) + H3CCHO + 2H+
(2)
Pd(0) + 2Cu(II)
- Pd(II) + 2Cu(I)
(3)
2Cu(I) + 1/2 02
+ 2H+
- 2 Cu(II) + H20
(4 )
Net: CH2=CH2 +
1/2 02
- CH3CHO
(5)
Water is the direct oxidant here, even though C>2 is consumed.
Dioxygen is reduced to by Cu(I), which reforms the Cu(II)
necessary for oxidizing Pd(0) to Pd(II). Other processes
which are thought to proceed in a similar manner are referred
to as having a "Wacker" mechanism.
Mimoun and co-workers put forth great effort to rule
out a Wacker-type mechanism for reaction 1. Several
experimental observations could not be rationalized by a
20
Wacker mechanism. Thus, despite apparent similarities
between Mimoun's system and the earlier rhodium/copper
catalyzed system which is reported to have a Wacker-type
27
mechanism, the differences are great enough to rule out the
hydrolysis process found in Wacker chemistry for Mimoun's
system.
Mimoun proposed that the catalyst in the Rh(III)/Cu(II)
oxidation system is a rhodium(I) complex produced from the
ethanol reduction of RhCl^ and Cu(II) in the initiation step
shown in reaction 6.


7
RhCl3 + 2CH2=CHR + Cu(C104)2 + 1.5CH3CH2OH ^
[Rh(CH2=CHR)2]C104 + CuCl(s) + HC104 + 2HC1 +
1.5 CH3CHO (6)
The observations which lead to this proposal by Mimoun
are the following: (1) active catalysts are formed by using
[Rh(CgH14)2C1]2 in the presence of 2 equivalents of HC1
instead of RhCl3*3H20; (2) an amount of acetaldehyde
approximately equal to the moles of catalyst used is produced
from ethanol oxidation at the beginning of the catalytic
reaction; and (3) 85% of the Cu(II) precipitates as CuCl at
the beginning of the catalytic 1-hexene oxidation.
Initiation of the catalysts would then be possible by the
binding of dioxygen to the reduced rhodium species. From
reaction 6 it can be seen that there are at least two
possible needs for an equivalent of Cu(II) to produce the
best catalytic conditions. The copper(II) is either
necessary for the reduction of RhCl3-3H20 to Rh(I) with the
stoichiometric production of CuCl, or for the removal of
chloride ion from solution to yield a more unsaturated
rhodium center. A combination of both roles for copper is
possible, and Mimoun did not eliminate some other possible
need for copper.
The mechanism Mimoun proposed involves a metal centered
oxygen atom transfer involving coordination of dioxygen and


8
olefin to the rhodium(I) cation from reaction 6, a
rearrangement to a peroxometallocycle, and then a decom
position to the rhodium(I) complex and the oxidation
products. Figure 1 shows this mechanism. It was based upon
Mimoun's suggestion that the active catalyst was a rhodium(I)
complex that led to the preparation of a silica gel organo-
sulfide supported rhodium(I) complex. This heterogenized
complex produced an active and stable catalyst for the
2 8
oxidation of 1-hexene to 2-hexanone (vide infra, Chapter
III) .
Results and Discussion
Characterization of the Catalyst as a Rhodium(III) Chloride
Complex
The rhodium carbonyl dimer (A), [Rh(CO)2C1]^, was
selected as the catalyst precursor due to the facile loss of
the CO ligands in the presence of 0^, the presumed need for a
rhodium(I) catalyst to coordinate 0^ and olefin, and the
usefulness of the CO ligands for infrared analyses.
Employing A as a homogeneous catalyst for reaction 1 at
various chloride concentrations and in the presence of Cu(II)
at 70C, the data in Figure 2 were obtained. Note that the
maximum initial 1-hexene oxidation rate (indicated by the
amount of 2-hexanone produced) is achieved using a
chloride/rhodium mole ration of 3:1, as was originally


Figure 1.
The mechanism proposed
for the Rh(III)/Cu(II)
oxidation of 1-hexene
by Mimoun to account
catalyzed 0~
to 2-hexanone.


10
RhCl


Figure 2.
Effect of increasing the chloride/rhodium
ratio on the initial rates and catalyst
stabilities for the C>2 oxidation of 1-hexene
at 70 C and 52 psi 0^7 in the presence of one
equivalent of Cu(II)7


mmole 2-he xa none
£* CD ro Si
ZT
EFFECT


13
reported for this system at 40C. However, increasing the
chloride/rhodium ratio to 5:1 at 70C causes a considerable
increase in catalyst stability with little change in the
initial rates, in contrast to the result obtained at 40C,
where a large drop in activity was found for the 5:1 ratio.
(For example, after 20 h at 70C with a 3:1 Cl/Rh mole ratio,
the catalytic activity is only 7.5% of the initial value,
while after the same time period with a 5:1 Cl/Rh ratio the
activity is 34% the initial rate.) Increasing the
chloride/rhodium ratio to 10 causes an even further increase
in catalyst stability at 70C (the activity after 20 h is 51%
of the initial rate). A similar beneficial effect of
increasing the Cl:Rh ratio to 5:1 was observed in analogous
experiments with Cu(II) absent. This suggests that a
specific interaction of chloride with rhodium and not copper
leads to catalyst improvement. Furthermore, the marked
dependences of both initial rate and catalyst stability on
such large chloride concentrations suggest a rhodium(III)-
chloride interaction. These results, along with others to be
presented, indicate that a rhodium(III) chloride complex is
the catalyst or the immediate precursor.
Experiments were conducted investigating the effect of
dioxygen pressure on 1-hexene oxidation at 70C. The use of
[Rh(CO)2C1 12/ H2S04 and NaC1 to catalyze the production of
2-hexanone from 1-hexene can be accomplished in the absence
of Cu(II). These results, along with the existence of an
induction period, are shown in Figure 3. Also demonstrated


Figure 3.
Demonstration of the dependence of the length
of the induction period on the pressure of
02, in the absence of Cu(II) at 70 C,
using [RMCOJ^Cl]- as precursor. The 02
pressures are ror A, 3.7 atm; B, 1.9 atm; C7
1.4 atm; and D, 1.0 atm.


15
c
o
2 0
hours
i
120


16
is the first-order dependence of the induction period on
dioxygen pressure. During the induction period the solution
color changes from light yellow (the color of [Rh(CO)2C1]2)
to bright orange (normal for rhodium(III) chloride
29
complexes). No induction period is seen when RhCl^,3H20
is used rather than A, nor when 0.1 equivalent or more of
Cu(II) is added to the reaction mixture. A proposal
suggested by these experiments is that of the dioxygen
oxidation of [Rh(CO)2Cl]2 to a rhodium(III) chloride complex
(which is either the active catalyst or an immediate
precursor) during the induction period.
Further investigation of this system involved the
reaction of A, dioxygen, and HC1 in ethanol, at 40C in the
absence of 1-hexene substrate. A bright orange complex (C)
was isolated as RhCl^(H20)2CH^CH^OH after 12 hours of
reaction. This process is described by reaction 7.
[Rh(CO)2 C1]2 + 4HC1 + 202 + 4CH3CH2OH -
2RhCl3(H20)2-CH3CH2OH + 2CH3CHO + 4CO (7)
The rhodium product (C) was characterized by elemental
analysis, molecular weight determination, and its infrared
and visible spectra. ^ The stoichiometry for reaction 7 was
verified in both [Rh(CO)2Cl]2 and HC1, but this was not
possible for C>2, CH3CH2OH, and CINCHO due to the catalysis of
reaction 8 by C (vide infra). The addition of an equivalent


17
2CH3CHROH + 02 -* 2CH3CRO + 2H20 (8)
R = CH3 or H
of Cu(II) or the use of [Rh ( CgH^ ) 2C1 ] 2 as the rhodium(I)
precursor considerably speeds up reaction 7 (vide infra) but
does not affect its outcome. Compound C catalyzes the
oxidation of 1-hexene to 2-hexanone as efficiently as
RhCl3'3H20 and without the occurrence of the induction period
observed when using [Rh(CO)2Cl]2 as the catalyst precursor
under identical conditions (see Figure 3). The observed
solution color changes and other results described above
indicate that under reaction conditions for the catalytic
oxidation of 1-hexene (reaction 1), the rhodium(III) complex
(C) is produced from the oxidation of [Rh(CO)2C1]2. An
explanation for the role of copper(II) and a more detailed
study of reaction 7 will be discussed in the second part of
this chapter.
To rule out the possibility that RhClg-3H20 (or C) may
be subsequently reduced to a rhodium(I) complex by alcohol
solvent to initiate catalysis (as proposed by Mimoun in
reaction 6), we investigated the initiation step using
RhCl3*3H20 and Cu(N03)2 -2.5H20 as precursors. For our study
we chose isopropyl alcohol as solvent since upon oxidation
this alcohol forms acetone which is much easier to
quantitatively measure than the more volatile acetaldehyde
(produced from ethanol). Using GLC, we found that in the


18
presence of 1 equivalent of Cu(II) only 0.5 equivalents of
acetone is produced immediately on mixing all reagents
necessary for the catalytic oxidation of 1-hexene and that
its concentration remains constant for at least 0.5 h. From
this result we can rule out the simultaneous reduction of
Rh(III) and Cu(II) proposed in reaction 6 because this would
require the oxidation of 1.5 equivalents of isopropyl
alcohol. We propose that reaction 9 initiates the catalytic
cycle for this system
Cl" + Cu2+ + 0.5(CH3)2CHOH
1 atm C>2 at 40C
isopropyl alcohol
1-hexene
CuCl. + 0.5 (CH-,) C0 + H +
( s ) 3 2
(9)
when RhCl3-3H20 is used as the catalyst precursor. Our
proposal requires that only enough reducing equivalents are
2 +
provided by isopropyl alcohol for the reduction of Cu to
form CuCl. Copper(I) chloride may be isolated from the
reaction mixture in 85% yield without affecting the catalytic
oxidation.


19
Mechanism of the 0-, Oxidation of [Rh (CO) C1 K to Rhodium(III)
Chloride
The oxidation of [Rh(CO)2Cl]2 (A) to rhodium(III)
trichloride (C) by 02 was originally studied because of our
interest in characterizing the active catalyst for the
Rh/Cu-co-catalyzed 1-hexene oxidation (reaction 1).
Copper(II) was excluded in these initial investigations to
facilitate the interpretation of the electronic absorption
spectra, elemental analysis and molecular weight data. The
substrate 1-hexene was excluded from these solutions to avoid
its catalytic oxidation to 2-hexanone after the formation of
the rhodium(III) chloride product. As described in the
previous section, the exclusion of Cu(II) and 1-hexene during
these studies proved to be quite useful for characterizing
the rhodium catalyst. The oxidation of [Rh(CO)2Cl]2 to
rhodium(III) chloride was generally monitored by electronic
absorption spectroscopy in order to determine the reaction's
end point. In the course of these studies it was found that
at elevated C>2 pressures (3-5 atm) an unusual intermediate
exhibiting a visible absorption band at 385 nm could be
detected. This observation led to a detailed investigation
of the mechanism of the C>2 oxidation of [Rh(CO)2Cl]2 to
rhodium(III) chloride in reaction 7, and the results are
presented below.
The electronic spectral changes accompanying the
oxidation of the [Rh(CO)2Cl]2 (A) to rhodium(III) chloride
(C) in the absence of both Cu(II) and 1-hexene is shown in


20
Figure 4 as a series of spectra recorded over the course of
the reaction. The growth and decay of an intermediate (B)
with an absorbance at 385 nm is noted. The charge-transfer
band beginning at the shortest wavelength is a result of A,
while the band at 480 nm is produced by C. As shown in
Figure 5, intermediate B is more stable in the presence of
excess Bronsted acid (8HC104/A). The presence of two
isosbestic points (at 377 and 435 nm) in both Figures 4 and 5
suggests the formation and subsequent reactivity of only one
intermediate. The isosbestic point at 377 nm is a result of
the reaction of A to form B at the beginning of reaction 7
(before much final product C has been formed). Early in the
reaction the decomposition of B to C becomes quite
pronounced, and this point disappears. The second isosbestic
point emerges at 435 nm when all A has been consumed and
results from the exclusive reaction of B to form C.
The initial rate of formation of B was found by visible
spectroscopy to follow the rate expression shown in eq. 10,
k[H+][02]
(10)
which is independent of the concentration of A. The
zero-order dependence on [A] rules out a mechanism involving
initially the formation of a rhodium hydride followed by the
insertion of dioxygen to form a rhodium hydroperoxide
intermediate, which occurs with [RhH(CN)4(H20)],
31e
and is


Figure 4. Series of visible spectra resulting from the
02 oxidation of [Rh(CO)2Cl]2 at 40C in the
absence of any HC1CK. Initial Rh(C0)2Cl
is 0.98 x 10 M. Spectra were recorded over
a 12 hour period.


absorbance


Series of visible spectra resulting from the
C>2 oxidation of [RhiCCD^ClL at 40 C in the
presence of 8 equivalents HC10., but other
wise same conditions as used for data
presented in Figure 4.
Figure 5.


absorbance


25
32
proposed in two other studies. The rate law in eq. 10 is
surprising because it indicates that the initial step or
steps in reaction 7 (those including and preceding the
rate-determining step) involve a reaction between H+, 0^, and
possibly CH^CI^OH, forming an intermediate oxidant which
subsequently reacts with [Rh(CO)2CI]2
We investigated the possibility that peroxide could
play the role of direct oxidant in reaction 7. This was
confirmed by experiments involving the titration of A with
HOOH to form C in the absence of dioxygen, monitored by
visible spectroscopy (reaction 11, in which S' is solvent).
[Rh ( CO) 2C1 ] 2 + 4HC1 + 2H00H + S' -*
2RhCl3(H20)2S' + 4CO (11)
Because HOOH slowly disproportionates or is reduced in
ethanol, as well as being consumed in a competing side
reaction (vide infra), the oxidation of A to C in this
solvent goes to only 70% completion. Very significantly the
oxidation of A by HOOH proceeds with the formation of the
same intermediate [B] as produced with 02 as oxidant,
indicating that reaction 11 and reaction 7 occur through
similar mechanisms. The kinetic rate law for reaction 11 was
determined by using Fourier transform infrared spectroscopy
(FT-IR) to monitor the consumption of A, and is shown in
equation 12. Several reports describe the reaction between a


26
-d[A]/dt = k([Rh(CO)2C1]2)[HOOH] (12)
metal complex and peroxide to form a coordination
compound. ^ The reaction in eq. 11 proceeding as
described above would exhibit the rate law shown in eq. 12.
On the basis of these arguments and those that follow, we
propose that intermediate B results from the coordination of
HOOH to Rh(CO)^C1]2 A proton NMR analysis at -70C showed
no evidence for B possessing a hydride ligand. Any hydride
species generated from the oxidative addition of HOOH to A
apparently are acidic, and fast exchange of all protons with
the alcohol solvent is very likely occurring.
The characterization of B was assisted by an FT-IR
spectroscopic study of reaction 11. Immediately on adding
HOOH to a solution of A and HC1 in ethanol, the formation of
a complex exhibiting a CO stretching band at 2102 cm ^ is
observed, and this band increases in intensity at the expense
of the bands due to A (at 1995 and 2069 cm ^; Figure 6). The
growth and subsequent decay of the CO band at 2102 cm ^ was
found to correlate directly with the band due to B at 385.nm
observed in the electronic absorption spectra. Therefore,
intermediate B retains one CO ligand. The assignment of the
band at 2102 cm ^ to coordinated CO was confirmed by use of
^CO in the experiment.
That B is a hydroperoxo rather than a u-peroxo complex
is evidenced by our ability to substitute tert-butyl
hydroperoxide (t-BuOOH) for HOOH in reaction 11 to obtain a


Figure 6
Series of infrared spectra obtained from the
HOOH oxidation of [Rh(CO)2Cl]2 in ethanol.
(A) Spectrum of [Rh(CO)-,CI] Reaction was
Spectrum L ¡
run using 0.84 x 10 M[RhfCO)_Cl] 2.
Spectra were recorded at (B) 0.25 hours
0.55 hours; and (D) 1.83 hours.
(C)


28


29
much slower reaction and the formation of an intermediate
analogous to B with an electronic absorption band at about
385 nm^ and an infrared CO stretch at 2099 cm ^, 3 cm"'*'
lower than that found for B with HOOH. Since t-BuOOH is not
known to bridge two rhodium species in the y-peroxo
configuration, we suggest that B is not a y-peroxo complex.
Only a limited number of stable hydroperoxide and alkyl
peroxide complexes of the platinum metals have been reported5
(not including those with Schiff base or bio-type ligands),
and some of these are capable of oxidizing terminal olefins
3 X ^ b
to 2-ketones. Intermediate B is only formed in the
presence of HC1 and is not formed on substituting either
HC104 or N(C2H<- ) 4C1 *H20 for HC1. Thus, both a proton and an
additional chloride are required in the formation of the
intermediate. We propose that intermediate B is
H2 [Rh(CO)Cl2~ (OOH)], produced as shown in eq. 13. Use of
the oxidation
[Rh(CO)2Cl]2 + 2HOOH + 2HC1
2H2[Rh(CO)Cl2(OOH) ] + 2CO (13)
state formalism to describe these species is potentially
misleading. An oxidative addition of HOOH to a Rh(I) complex
produces HRhIIIOOH. Deprotonation generates Rh^OOH After
a number of attempts, we have not been able to observe the
0-0 stretch between 800 and 900 cm 1 expected for a
coordinated peroxo group in the infrared spectrum. This is


30
due to the low concentrations necessary to stabilize this
intermediate, the poor window in this region of the infrared
spectrum for ethanol solvent, and the hydrogen bonding in
this system which would broaden this band. When the
intermediate is generated with 0^ and excess 0, is removed, it
spontaneously decomposes to rhodium(III) chloride over
several hours. This is consistent with the formulation of
this intermediate as [Rh(CO)Cl^(00H)], for this species
possesses two oxidizing equivalents in the peroxo (or
hydroperoxo) ligand.
Intermediate B is not formed in the absence of HC1 in
reaction 11, but the reaction in eq. 14 occurs under argon in
ethanol solvent,
Ar
[Rh (CO) 2 C1 ] 2 + HOOH 2C02 + D (14)
producing free CO^ from the oxidation of a CO ligand and a
very deep brown rhodium(I) complex (D) exhibiting a broad CO
stretching band at 2048 cm Thus, [Rh(CO)2Cl]2 could be
reformed from D by exposure to a CO atmosphere, and the
production of CO^ from the CO oxidation by HOOH is catalytic
in A in a CO atmosphere. This reaction has been previously
3 4
reported in benzene, where D precipitates. It is
3 4
reported that redissolving this solid in ethanol and
exposing it to CO leads to the formation of a rhodium(I)
carbonyl complex with a spectrum similar to A. Reforming
[Rh(CO)2Cl]2 from D under CO is significant because it


31
indicates that D is a rhodium(I) complex and that the
irreversible oxidation of rhodium(I) to rhodium(III) by HOOH
in ethanol is slow relative to the oxidation of the CO
ligands to C02 (which takes several hours). These results
further suggest that in the presence of HC1 the reaction
between A and HOOH produces the relatively stable rhodium(I)
hydroperoxo coordination complex B as an intermediate. In
the presence of HC1 reaction 3 is faster than reaction 14,
and the majority of HOOH is consumed to form B rather than
C02 and D. That reaction 14 does occur to a small extent in
the presence of HC1 can be seen in Figure 6, in which the
band at 2334 cm ^ due to C02 is evident. This competing
reaction accounts, at least in part, for the incompleteness
noted for the titration of A with HOOH in reaction 11.
The stabilization of B by excess Bronsted acid,
evidenced by a comparison of the electronic absorption
spectra in Figures 3 and 4, can be explained by considering
the deprotonation of the RhOOH group as the initiation step
for the reaction of B to form C. A further investigation of
the decomposition characteristics of B also proved to be
useful. Upon isolation of a mixture of B and C by quick
evaporation of a dilute solution to dryness under vacuum, B
decomposes within a minute to a wet solid. An infrared
spectrum of this product revealed a large concentration of
water in addition to a high-energy CO stretching band at
2132 cm 1 (shifted from 2102 cm 1 for B). These are the
results expected from the fast, autocatalytic decomposition


32
of a hydroperoxo complex. The reduction of the hydroperoxo
ligand by Rh(I) will produce and a rhodium(III) carbonyl.
This oxidized metal complex will be much poorer at
back-bonding into the CO than was the rhodium(I) in B, and
therefore its stretching frequency would be shifted nearer to
that for free CO (at 2143 cm 1). Finally, in Figure 7 are
presented data which illustrate the effect of increasing the
rhodium concentration on the rate of decomposition of the
intermediate. This rate was measured by monitoring the
electronic absorbance for C at 480 nm. It is evident that at
a threshold concentration in A between 0.98 x 10 ^ M and 1.47
x 10 3 M, the reaction of B to form C becomes autocatalytic
in character. At 0.98 x 10 3 and 0.68 x 10 3 M this reaction
follows a much more regular course. These results indicate
that a free radical decomposition of intermediate B is a
sustained process only above the threshold rhodium
concentration. Indeed, the electronic absorption spectra
indicate that at much high concentrations, reaction 7 is less
specific to the exclusive formation of C. In this case the
band at 480 nm for C is present only as a plateau due to the
absorbance of a secondary rhodium(III) product which absorbs
at lower wavelengths.
The characterization of intermediate B and the rate law
in eq. 10 have an importance not yet discussed. They
indicate that in reaction 7, hydroperoxide is initially
formed from the Bronsted acid catalyzed reduction by dioxygen
by ethanol or isopropyl alcohol solvents (eq. 15). The


Figure 7.
Demonstration
of RhCl
of
>CH
,(H20) 2 4
concentration (profile
in
(B)
Rh(CO)pCl
0.98 xKT
the autocatalytic formation
-jCH^OH above the threshold
A). Concentrations
are for (A) 1.47 x 10,'' M;
M; and (C) 0.68 x 10 j M.


Absorbonce


35
CH3CHROH + 02 - CH3CRO + HOOH (15)
R = CH3 or H
oxidation of primary and secondary alcohols to aldehydes and
ketones using dioxygen has been known for some time.'*5'^
These oxidations may be divided into two categories: (1)
free radical initiated reactions, using asoisobutyronitrile
(AIBN) for example, and (2) metal-catalyzed oxidations. The
principal difference is that oxidations of the first type may
9
produce HOOH stoichiometrically (eq. 15) as long as
precautions are taken to stabilize hydrogen peroxide while
oxidations of the second type produce waterd (eq. 8),
because the metals which catalyze HOOH formation also
catalyze decomposition of hydroperoxides to H20 and 02 very
efficiently. Thus, there is literature precedence supporting
our proposal that HOOH is produced (albeit inefficiently)
37
with a Bronsted acid as a catalyst.
Under our reaction conditions the HOOH concentration
reaches a very low steady-state value, accounting for the
slow initial rate of oxidation of A (eq. 7) and our inability
to detect HOOH by iodometric techniques in acidic ethanol
solutions under 0^. However, we have obtained indirect
evidence of HOOH production in two series of experiments in
which H+, Cu(II) and Rh(III) were checked for their ability
to (1) speed up the oxidation of A (eq. 7) by producing HOOH


36
catalytically from the alcohol reduction of C>2 and (2)
catalyze the oxidation of isopropyl alcohol (eq. 8) as
measured by acetone production. For the investigation of the
effect of these three reagents on the rate of oxidation of A
(eq. 7), we worked at 1 atm rather than at 80 psi of 02
(5.4 atm) because the reaction is much slower at this reduced
pressure. As shown in experiment D in Table I, no final
product is observed at 480 nm in the electronic absorption
spectra in the absence of HC104, Cu(II) or Rh(III) after 1
hour, and the reaction take 36 hours to come to completion.
In contrast, the addition of 0.1 equiv of Cu(II) or Rh(III)
at the beginning of the oxidation of A (eq. 7) results in a
much faster reaction, with Cu(II) being most efficient
(experiments A and B). Doubling the acid concentration also
speeds up the reaction but to a much lesser extent
(experiment C). From these data it appears Cu(II) and
Rh(III), and to a much lesser extent H+, catalyze the
production of HOOH from ethanol reduction of 0^, and this
causes the increased rates observed for the oxidation of A
(eq. 7) in their presence.
Substantiation of this was found from our investigation
of the effectiveness of Cu(II), Ru(III) and H+ in catalyzing
the oxidation of isopropyl alcohol (eq. 8). Their
effectiveness at the beginning of this reaction follows the
order Cu(II) 'v Rh(III) >>H+, with rhodium resulting in 19
turnovers (acetone/rhodium) in 25 h and H+ producing only a
3 8
trace amount of acetone. The consumption of dioxygen when


37
Rh(III) was used for reaction 8 was also followed on a gas
burette for several hours and is linear over that time,
indicating this catalyst is not slowly .rendered inactive. It
is reasonable to suggest that HOOH, or peroxo metal
complexes, are formed as intermediates in reaction 8 and that
the efficient catalysis of this oxidation is evidence of
the ability of a reagent to catalyze the production of
peroxide from the alcohol reduction of 02. Because both
Cu(II) and Rh(III) are efficient hydroperoxide decomposition
catalysts, the HOOH is produced at a very low steady-state
concentration and may in fact never leave the coordination
sphere of the catalysts.
Experiment E in Table I demonstrates unequivocably that
an intermediate oxidant (HOOH) is formed in the presence of
only HCl, HC104, ethanol, and 0^. This has been labled an
"incubation" experiment because it involved stirring 3.2 x
10 ^ M each of HCl and HC10. in ethanol under 1 atm of 0_ at
4 2
40C for 48 hours, followed by the addition of the [Rh(CO)2~
C1 ]2 to initiate reaction 7. In this case upon adding A no
induction period was observed and the reaction was complete
in only 7 hours compared to the 36 hours necessary when
mixing all reagents from the start. In agreement with the
rate law in eq. 10, this further indicates that the first
step in the oxidation of A involves the production of HOOH
from H+, 02 and CH^CH^H and that hydroperoxide is the
reagent directly responsible for the oxidation of [Rh(CO)2~


38
Table I. Oxidation of [Rh(CO)2C1]2.
Experiment
Catalyst3 at
Relative
Absorbance
for Complex C
480 nm at 1.0 h
Time for
Completion of
Reaction 7
A
0.15 mM Cu(II)
14
4
B
0.17 mM Rh(III)
3
10
C
4.2 mM HC104
ob
14
D
None
0
36
E
"Incubation"0
1
7
aThese reactions were run at 40C and 1 atm of 02, using
0.80 x 10-3 M [Rh(CO)2C1]2, 3.2 x 10*3 M HC1, and 22.5 mL of
ethanol as solvent, in addition to the catalyst listed.
bNo final product II could be detected after 1.0 h.
c 3
This run involved stirring 3.2 x 10 M HC1 and
3.2 x 10 3 M HCIO^ in ethanol at 40C and 1 atm of 02 for
48 h, followed by the addition of [Rh(CO)9C1]2 to a
0.90 x 10
M concentration.


39
Cl]2 to rhodium(III) chloride in ethanol via a hydroperoxo-
rhodium complex intermediate. Our proposed mechanism for
this oxidation is shown in Scheme I and is substantiated by
all of the preceding evidence and arguments.
Scheme I
CH3CHROH + 02 CH3CRO + HOOH (a)
[Rh ( CO) 2C1 ] 2 + 2HC1 + 2H00H
2 [Rh(CO)Cl2(00H) ]2_ + 4H+ + 2C0 (b)
[Rh(CO)Cl2(00H)]2_ + 2H+ [Rh(CO)Cl2(00)]3~ + 3H+ (c)
[Rh(C0)Cl2(00) ]3_ + 4H+ + Cl" + CH3CHR0H -*
RhCl3(H20)2CH 3CHR0H (d)
An intermediate analogous to B is not produced when
[Rh(CgH^4)2C1]2 is used instead of [Rh(CO)2Cl]2 as the
rhodium(I) starting material in a reaction similar to that in
eq. 7. In this case the reaction to form rhodium(III)
chloride is complete in only 40 min (compared to 12 hours
under identical conditions with A), and no evidence for
intermediates is found in the electronic absorption spectra.
In contrast, [Rh(P(tolyl)3)(CO)Cl]2 is not oxidized to
rhodium(III) chloride even after 48 hours.


40
Since Scheme I requires solvent reducing equivalents to
produce HOOH and subsequently [Rh(CO)CI2(OOH)] from 0^, any
solvent capable of this 02 reaction could lead to the
oxidation of A by this mechanism. Indeed, we have found that
methanol, ethanol, isopropyl alcohol, and to a lesser extent
tetrahydrofuran (THF), all produce B as an intermediate in
the oxidation of A by 0^. In THF this could appear through
the intermediacy of THF hydroperoxide, produced from the
abstraction of an a-hydrogen atom by and a subsequent
radical coupling reaction. The THF-hydroperoxide may react
with [Rh(CO)2CI]2 as both HOOH and t-BuOOH. In contrast,
use of the typically nonreducing solvents tert-butyl alcohol,
39
acetone, and N,N-dimethylformamide (DMF) does result in
oxidation of [RhtCO^Cl^ without forming B as a stable
intermediate. In tert-butyl alcohol and acetone the reaction
is very fast, finishing in 40 min under conditions for which
it takes 10 hours for completion in ethanol. In DMF the
reaction is much slower (also taking 10 hours) and was
monitored by electronic absorption spectroscopy. In this
solvent only one isosbestic point is observed (at 390 nm) due
to the production of rhodium(III) trichloride from the
oxidation of [RhiCO^Cl^ without the formation of any stable
intermediates (Figure 8).
It is interesting that the oxidation of A (eq. 7)
proceeds through the coordination of HOOH to [RhCCO^Cl^ in
primary and secondary alcohol solvents rather than proceeding


Figure 8. Series of visible spectra for the 0^
oxidation of [RhiCOi^Cl]^ to rhodium(III)
trichloride in DMF as solvent.




43
by the alternative mechanism that seems to occur in tert-
butyl alcohol, acetone and DMF. When THF is used as solvent
the reaction is much faster and only poor resolution of the
electronic absorption band due to B is observed. This is due
to a lower concentration of B relative to that found in the
alcohols, and possibly a low energy absorption band.40 In
THF it may be that both mechanisms are functioning, which
would explain the low concentration of B observed. It is
important to note that we cannot rule out the alternate
mechanism occurring in methanol, ethanol, and isopropyl
alcohol solvents to a small degree. However, it is evident
from the magnitude of the bands due to B in the electronic
absorption and infrared spectra, as well as data from the
kinetic rate law in eq. 10, that Scheme I involving the
coordination of HOOH to [RhiCO^Cl^ is dominant in primary
and secondary alcohols.
Conclusion
It is usually necessary to include bio-type or
Schiff-base ligands in order to prepare a hydroperoxide
complex, which makes the characterization of B as [Rh-
(CO)Cl^(OOH)] noteworthy. The CO ligand seems to be
responsible for at least some amount of the stability of this
complex. It is this stability which does not lead to the
characterization of the complex as an intermediate in the
catalytic oxidation of 1-hexene to 2-hexanone. Complex B


44
appears to have only slight (if any) reactivity as a catalyst
for 1-hexene oxidation. This result is not unexpected when a
comparison is made between the rhodium(III) active catalyst
and the rhodium(I) hydroperoxo complex, B.
The fact that primary and secondary alcohols can form
low concentrations of HOOH from the reduction of 02 may also
have several implications. Other metal complexes may have to
be included with H+, Cu(II) and Rh(III) as catalysts for the
alcohol reduction of 0^ to HOOH. Systems which require long
term exposure to alcohol and 0^ may find the low
concentrations of HOOH produced to be quite significant.
Substrate oxidations of 0^ via HOOH formation may also be
more prevalent than now realized.
Further results have shown HOOH and t-BuOOH to both be
effective reagents in the RhCl^3H20 catalyzed oxidation of
1-hexene to exclusively 2-hexanone in the absence of 0^. The
results are the same whether the solvent is ethanol or tert-
butyl alcohol (which has no reducing equivalents). These
facts provide still further justification for the character
ization of the active catalyst for reaction 1 as a
rhodium(III) chloride complex.
Experimental Section
All solvents and reagents were of reagent grade and
used without further purification. Literature methods were
used to prepare [Rh(CO)2C1]2.41 Hydrogen peroxide and tert-
41


45
butyl peroxide were used as 30% and 70% aqueous solutions,
respectively, and were standardized iodometrically. The
acids HC1, H2S04, and HC104 were used as their concentrated
aqueous solutions.
Infrared spectra were recorded on a Nicolet 7000 Series
Fourier transform infrared spectrometer. GLC spectra were
obtained with a Varian Model 940 FID instrument using a
3-m,l/16 in. i.d. copper column packed with Chromasorb P
supported diethylene glycol adipate. For the detection of
acetone a column temperature of 60C was employed, and the
measurement of 2-hexanone was quantitated by using
2-heptanone as an internal standard. The electronic
absorption spectra were recorded on a Cary 14, and all
samples were run in air at ambient temperature and pressures.
Care was taken to verify that the intermediates monitored by
this technique were stable over the course of the measure
ments. The molecular weight of C was determined in methanol
by vapor pressure osmometry.
Catalytic Oxidations of 1-Hexene
All catalytic 1-hexene oxidations were run in 250-mL
Parr pressure bottles equipped with bras Swagelok pressure
heads. These were constructed to allow purging with C>2, as
well as sampling of the solution under reaction conditions
during the course of the reactions. 2-Hexanone production
was measured by GLC.
A typical catalytic reaction was run as follows: to a
250-mL Parr bottle were added 0.074 mmol of [Rh(CO)' ]BF.
L 2 n 4


46
2
(prepared as earlier reported and used immediately),
0.0171.g of Cu(N03)22.5H2 (0.074 mmol), 0.0219 g of NaCl
(0.375 mmol for the case in which 5:1 mole ratio chloride/
rhodium was desired), 0.41 mL of 0.36 M H2SC>4 (0.148 mmol as
an ethanol solution prepared from aqueous concentrated
H2S04), 0.568 mmol of 2-heptanone, 45 mL of absolute ethanol,
and 15 mL of 1-hexene (purged through alumina to remove
peroxides). This mixture was purged 5 times with 60 psi of
02, set to 40 psi of C>2, and the reaction initiated by
placing in a 70C oil bath.
Preparation of RhCl^(H20)2CH3CH2OH (II)
Compound C was prepared for characterization studies
most easily under 40 psi of 02 at 70C by mixing 0.0514 g of
[Rh(CO)2Cl]2 (0.132 mmol), 1.10 mL of 0.48 M HCl (in ethanol,
0.528 mmol), and 15 mL of ethanol. This produced a bright
orange solution after a reaction overnight, from which C was
isolated by rotovapping to dryness and drying in vacuo. The
for H402Cl3Rh caled. 245; found, 226. Anal. Caled for
C2H103C13Rh: C' 8*24; H' 3.46; Cl, 36.50. Found: C, 8.41;
H, 2.69; Cl, 37.17.
Determination of Acetone Production
In Presence of 1-Hexene. The measurement of acetone
produced in the initial stage of the Rh/Cu-catalyzed
oxidation of 1-hexene with isopropyl alcohol as solvent was
made by GLC as follows: To a 50-mL round-bottom flask were


added to 0.159 g of RhCl^'Sf^O ( 0.605 mmol), 0.137 g of
Cu(NO^)2'2.5H20 (0.589 mmol), and stir bar. This was purged
20 min with 02 at 40C and 30 mL of an C^-purged, 9/1 (v/v)
solution of isopropyl alcohol/l-hexene added to initiate the
reaction. GLC's were recorded after 4, 8, 17, 25 and 40 min.
The amount of acetone produced was determined by comparison
of peak heights with standards at the same time under
identical conditions. When this 1:1 Cu/Rh ratio was used,
0.5 mol of acetone was formed per mole or rhodium in the
first 4-8 min. No further production was observed. When a
2:1 Cu/Rh mole ratio was used, continuous, catalytic
production of acetone was observed.
In Absence of 1-Hexene. The catalytic production of
acetone from the 02 oxidation of isopropyl alcohol was
observed when 1-hexene was excluded from the solutions. Both
RhCl^'S^O (0.140 mmol) and a stir bar were placed in a 15-mL
round-bottom flask and purged 20 min with 02 at 40C. Into this
was syringed 7 mL of isopropyl alcohol, purged itself with
02 at 40C, to initiate the reaction. Acetone production was
measured as described above.
Titration of [RhtCO^ClK with HOOH
Because the reaction of HOOH with Rh(CO)2Cl2 (A) is
quite slow in ethanol, it was run at 40C. The visible
spectrum of the intermediate, [Rh(CO)Cl2(00H)] (B), is not
clearly observed by first adding 1.0 equiv of HOOH, followed
an hour later by 0.5 equiv. The first addition causes the


48
reaction of much of the starting material A (which overlaps
the band at 385 nm), so that after the second addition the
band due to C at 385 nm is easily observable in the
electronic absorption spectrum. Intermediate B is easily
detected in the oxidation of A by HOOH by using FT-IR. Since
there is no overlap of the carbonyl bands of A and B, the
intermediate is detected in the first addition of HOOH.
Immediately after use HOOH was diluted in ethanol. Aqueous
dilution causes the addition of too much H20, which retards
the reaction considerably.


CHAPTER III
ENHANCED SITE ISOLATION ON SILICA GEL
AND IMPROVED LIFETIMES OF SITE ISOLATED CATALYSTS
Introduction
Functionalized polymers have been increasingly employed
to support transition metal complexes as catalysts in recent
years. There have been several reviews in the literature
involving both organic supports4^ 4^ and inorqanic
solids.4 50 The system of interest here involves
functionalized supports which usually contain molecularly
definable species. Such systems are largely in the minority,
because they do not include either (1) the deposition of
metals or metal oxides by the oxidation or reduction of metal
complexes, or (2) the intercalation of metals in
unfunctionalized inorganic oxides.
The lack of physical methods which can routinely
provide identification of surface supported metal complexes
hinders the development of new catalytic systems. As a
result, attempts to prepare supported catalysts are often
based upon known homogeneous systems. The approaches for
49


50
attaching metal complexes is often guided by the ligand
system of the homogeneous catalyst. The methods which have
been utilized include ligand exchange or substitution of the
51 5 2
metal complex to the support, addition to unsaturated
metal complexes,^^^ and ionic attachment. '>~> '^
Immobilization of metal complexes on solid supports can
provide advantages over both homogeneous and heterogeneous
catalysts. Included in these are (1) the ease of separating
solid catalyst from the reaction mixture, which encourages
the use of flow reactors, (2) the ability to greatly increase
dispersion of the metal on the surface, allowing the use of
less metal (and finances), and (3) reduced contact with the
reaction vessel leading to reduced corrosion. This potential
for gaining the advantages of both homogeneous and
heterogeneous catalysts has many industrial applications
which are being investigated.
Following below is a brief discussion of the general
properties of the inorganic solid, silica gel, which is used
as a catalytic support in the research presented in this
chapter.
Silica gel has a surface which is very irregular
consisting of hydroxyl and silicon bridging oxide groups. It
is quite rigid and contains many channels throughout its
structure and only the silica gel surface may be functional
ized. Silica gel samples which vary widely in surface area
are available. Several characteristics of silica gel make it
potentially preferable to organic polymers as a support for


51
metal complexes. The rigidity of its silicon oxide tetra-
hedra is often an advantage for immobilizing and site
isolating catalytic centers. The stability of silica gel at
higher temperatures than organic polymers may also be
important. Finally, the large number of organosilanes which
are becoming commercially available and the mild conditions
under which functionalization is achieved makes the number
of possible silica supported moieties quite large.
As mentioned above, organosilanes are employed to
functionalize the surface of silica gel. It has been
reported that the reaction proceeds by hydrolysis, hydrogen
bonding and final bond formation as shown in Figure 9 as
reactions a-c.57 The symbol [SG]-OH is used to represent
unfunctionalied silica gel.
An investigation of the nature of the binding of
5 8
organosilanes to the silica surface was recently reported.
Before this study was reported, it was generally believed
that three bonds from the silane to the silica suface were
formed. However, in this report Waddell et al. state that most
commonly only one bond is formed from silane to silica, while
the formation of two bonds is possible, and tridentate
bonding seems unlikely due to steric limitations.
Another important characteristic of polymer bound
metals is the ability to achieve site isolation of the metal
complex on the polymer surface. Solid supports can function
to avoid molecular aggregation and prevent the formation of
multinuclear complexes or clusters. This usually requires


Figure 9. General reaction scheme for the functional
ization of the surface of silica gel,
[SG ]-0H.


53
R3SiCl + H20
R3Si(OH) + HC1
(a)
R3S(OH) + [SG]-OH
[SG ]-0 H OH ( S i ) R 3
(b)
[SG ]-0--H OH(Si)R3
[SG ]-0(S)R3 + H20
(c)


54
dilution of active sites on the surface in order to minimize
contact of supported metal complexes, although another method
has been successful at achieving site isolation (vide infra).
Most of the work reported in supporting metal catalysts has
employed very large loadings of the polymeric surface with
the desired functional group and metal complex. In these
cases elemental analyses can often be utilized, which is
advantageous since there are so few physical methods avail
able. However, this has led to a lack of research on systems
with definite site isolation of active species, or possible
improvement of existing catalysts by the establishment of
site isolation. Rigid, non-flexible polymeric supports such
as silica gel are usually required when attempts to obtain
site isolation of a supported species are undertaken.
There are several reports of functionalized silica gel
being used to achieve site isolation, and perhaps other
examples from industrial laboratories which have not reached
any available literature. Among the reported examples are a
bound imidazole iron tetraphenylporphyrin which is used to
59
reversibly bind dioxygen, and cyclopentadiene groups
supported on silica gel which form stable mononuclear iron
and cobalt carbonyl complexes.^


55
Results and Discussion
Polymer Support of the Catalyst
The oxidation of terminal olefins to 2-ketones
catalyzed by rhodium and copper was discussed in some detail
in the previous chapter in relation to its homogeneous
mechanisms. Here will be described an investigation to
increase that catalyst's relatively short lifetime by
attempting to provide an ideal supported environment for the
catalytic species. Prevention of the suspected deactivating
oxidative aggregation of the rhodium catalyst was the
rationale for this approach.
Required of a solid support is a solvent independent
rigidity which could improve prospects for obtaining site
isolation. Silica gel, unlike organic polymers such as poly
styrene, meets these requirements. Initial attempts at using
an organosulfide ligand on silica gel to bind the
rhodium/copper cocatalysts were successful.^ Goals of
improving the activity and lifetimes of supported catalysts
while gaining a detailed knowledge of the silica surface
precipitated the research described in this chapter.
Silica gel supported organosulfide samples (abbreviated
[SG]-SH) were synthesized using (3-mercaptopropy1)trimethoxy-
silane [ (CH^O) ^Si ( CH2CH2CH2SH )] reacted with plain silica
gel. A simple model was used to help gain insight into the
surface coverage on the silica gel. Approximating the


56
silicon-oxygen bond distance as two Angstroms and assuming
tetrahedral coordination around silicon, then the distance
O
between oxygen atoms of the surface silanol groups is 6.5 A.
In order to obtain an upper limit it is assumed that a flat
surface exists and that all of the surface groups are
silanols (-SiOH). Since the Davison Grade 62 silica gel
2
employed has a surface area of 340 m /g [SG], then there is
-9
approximately one surface hydroxyl group per 4.3 x 10 m of
surface. Thus, it can be calculated that as an upper limit
there are about one mmol of surface silanol groups per gram
[SG]. With this value it can be calculated that the [SG]-SH
samples prepared contain approximately 1/40, 1/20, 1/10 and
1/5 mmol sulfide/mmol surface Si (S/Si) which correspond to
0.025, 0.5, 0.10 and 0.20 mmol S/g[SG], The number of mmol
S/glSG] was determined by electronic absorption for all
samples as described in the experimental section and is
independent of the model and calculations discussed above.
The values for the number of mmol S/g[SG] varied only a small
amount between preparations of functionalized silica gels.
It was these experimental values which were employed to
determine the amount of silica gel necessary for each
catalytic oxidation. The general labels used to represent
[SG]SH samples of different sulfide loadings are shown in
Table II.
Also worthy of consideration is the relatively large
potential surface area over which the supported rhodium
complex may cover due to its attachment to a chain of six


57
Table II. Representations used to designate [SG]-SH samples
of varying sulfide concentrations.
SH Loadings on [ SG ] Surface
0.025 mmole S/g [SG]
0.05 mmole S/g [SG]
0.10 mmole S/g [SG]
0.20 mmole S/g [SG]
1 surface -SH/ 40 surface
-SiOH
- 1S/20S
- 1S/10S
- IS/ 5Si


58
atoms. Despite not being linear, this chain still allows a
380 square Angstrom area over which each rhodium may migrate.
This number, along with the surface Si concentration, allows
the calculation that the silica surface must have a
concentration less than 1 S/g surface Si in order for site
isolation of the rhodium to exist. This is a convenient
number to which properties of actual [SG]-SH samples may be
compared.
Preparation of supported rhodium complexes on silica
gel was achieved by utilizing freshly generated [Rh(CO)2S' ]-
6 2
BF4 (S' = solvent) in ethanol or tetrahydrofuran (THF) as
shown in reaction 16.
[Rh(CO)2Cll2 + 2AgBF4 2[Rh(CO)2S' ]BF4 + 2AgCl (16)
This rhodium cation readily binds to lSG]-SH samples at room
temperature producing silica gels varying from bright yellow
to red-orange as the concentration of surface sulfide is
increased.
The carbonyl ligands in the rhodium complex bound to
the silica gel allows the use of infrared spectroscopy to
investigate the functionalized surface. In these studies
freshly prepared [Rh(CO)2S' ]BF4 (S' = solvent) was reacted
with [SG]-SH sample under nitrogen and an infrared spectrum
quickly taken. The supported rhodium complex produced on
many dilute functionalized gels (e.g., 1S/40S) yields a
two-band infrared spectrum ( 2055 and 2005 cm ^) characteristic


59
of [SG]SRh(CO)2S1 (S' = solvent). More concentrated
[SG]-SH samples (e.g., 1S/5S) treated identically produce
three-band spectra ( 2075(m), 2055(s), and 2005(s) cm-'')
5 2
indicative of a supported dimer, ([SG]-S)2Rh2(CO)4. These
different surface species are represented in Figure 10. It
seems very evident that concentration of surface sulfide
groups past a certain point removes site isolation and
permits supported rhodium dimerization. These trends and
their implications will be discussed further in later
sections.
Catalytic Oxidations of 1-Hexene by Supported Complexes
Silica gel organosulfide supports ([SG]-SH) as
described previously were used to immobilize rhodium and
copper in order to investigate in detail the heterogeneous
catalytic oxidation of 1-hexene to 2-hexanone (reaction 17).
I!
2CH2=CH(CH2)3CH3 + 02 2CH3C(CH2)3CH3
(17)
Electronic absorption (as described in the Experimental
Section) was used to quantify the amount of sulfide in each
silica gel sample. The amount of sulfide present determined
the quantity of [SG ]-SH used as a support in each catalytic
oxidation. Each oxidation to be discussed employs 0.074 mmol
of both [Rh(CO)_S' jBF. (S' = solvent) and Cu(NO,),3H,0.
2 n 4 3 2 2
The quantity of [SG]-SH which provides 0.16 mmol of sulfide


Figure 10.
Representation of the different supported
rhodium complexes obtained with (1) 1S/5S-
[SG ]-SH and (2) site-isolated 1S/20S-
[ SG ]-SH.


Si\/\/SH
1) .20mmole S/g(SG)
Si^Acu RhC?)2SnBF4
XSH A r
SVVSH RT
ElOH
Si^\X\sH
2) .OSOmmole S/g(SG
^Y-'SH
same
/n/^SH
(CC^Rh^ ^RhtX>2
-Si
A
CO)2Rh RhCC^
Si NS/
SRhC02Sn
sjW-SRh(CO)2S'n


62
sites (a 10% excess) is used in each oxidation. Also added
to each reaction were 2 equivalents of HC104 (based on moles
of rhodium), 15 equivalents of 2-haptanone internal standard,
45 mL absolute ethanol solvent and 15 mL 1-hexene substrate.
An apparatus of 250 mL Parr pressure bottles was used to
conduct the experiments along with a pressure head which
allowed the removing of aliquots of the reaction mixture
under reaction conditions. Reactions were initiated by
purging the pressure bottle containing all components of the
reaction five times with 60 psi 0^, setting the pressure to
40 psi C>2 and placing the apparatus in a 70C oil bath. The
HC10. was used because Mimoun found a Bronsted acid to be
4
necessary when using rhodium(I) in his homogeneous
investigation, and it is given a role in his proposed
mechanism. Gas-liquid chromatography (GLC) was employed to
follow the catalytic oxidations. A calibration curve of
2-hexanone product versus 2-heptanone standard was used to
calculate 2-hexanone production in millimoles.
In preparing [SG]-SH supports, if it is assumed that
all of the added (CH^O)3SiCH2CH2CH2SH reacts completely, one
obtained values for [SG]-SH of 0.025, 0.050, 0.100 mmol
S/g[SG] corresponding to 1S/40S, IS/ 20Si, and 1S/10S,
respectively. The analysis for sulfide (using a rhodium
complex and electronic absorption as in the Experimental
Section) for a series of [SG]-SH samples produces values of
0.020, 0.041, and 0.076 mmol S/g[SG]. These values are
reasonably close to those expected for complete reaction and


63
also have relative ratios to one another very similar to
those which assume complete reaction. Again, it is the
experimental values for sulfide content which are used in
determining the quantity of [SG]-SH necessary for each
catalytic oxidation.
Results of the heterogeneous catalytic oxidation of
1-hexene to 2-hexanone are most clearly displayed as graphs
of mmol of product (2-hexanone) versus time (in hours).
Figure 11 shows the oxidation results characteristic of three
[SG]-SH samples which vary in sulfide loading. The samples
are referred to by a ratio of sulfide to surface silicon
atoms in the silica gel. These values are obtained by
assuming complete reaction when functionalizing the gels.
However, the experimental sulfide concentration values were
always used when determining the mass of silica gel necessary
for reaction. Each curve in the oxidation graphs represents
many experiments repeated with the same supply of
functionalized silica gel. Also, other samples were prepared
and compared to previous gels. The experimental sulfide
concentrations were very similar between silica gel batches.
The idealized S/Si ratios are then used for convenience in
referring to several different supplies of similar silica
gels.
In Figure 11, if all of the rhodium and copper is
effectively site isolated on these samples, then very similar
activity should result from each of the catalysts. The
1S/40S (0.025 mmol S/g[SG]) sample, curve A, is less active


Figure 11.
Profiles for the oxidation of 1-hexene obtained at
70C using [SG]-SH supported rhodium catalysts with
various loadings of organosulfide. (A) 1 surface
sulfide/40 surface silanol groups, 1S/40S;
(B) 1S/20S; (C) 1S/10S.


time, hr
mmol 2-hexonone
ro
o
1
S 9


66
for 2-hexanone production than the 1S/20S and 1S/10S
samples (0.05 and 0.10 mmol S/g[SG]). This results from
diffusion problems which will be discussed further later in
this chapter. Curves B and C do show similar activity for 24
hours as shown. Catalytic activity resulting from immobili
zation of the rhodium and copper complexes on silica gel
certainly has been demonstrated, and several comparisons to
these results will be made in following sections.
After establishing supported activity, it is important
to check for leaching of the metal complexes from the solid
into solution. Catalytic oxidations were run for three hours
and the solutions removed by syringe under reaction
conditions. The filtrate, after measuring the volume, was
then placed in a new Parr bottle with another equivalent of
Cu(II) and the oxidation re-started in the original manner.
The filtrate had activity ranging from 5 to 15 percent of the
total normal supported activity depending on the silica gel
sample being studied. Since the homogeneous rhodium/copper
oxidation catalyst is much more active than the corresponding
supported system, then it is apparent that the vast majority
of the heterogeneous catalytic activity is due to [SG]-SH
bound catalyst.
It is relevant to stress that experiments to check for
leaching must be done under reaction conditions. The
chemical equilibria involved in leaching may be greatly
affected by conditions milder than those during reaction and


67
thus leaching should be investigated only under reaction
conditions.
Alkyl Covering of the Silica Surface to Improve Site
Isolation and Catalysis
The silica gel supported catalytic system as described
until this point offers several characteristics which make it
ideally suited for further investigation of site separation
in a quantitative manner. Already demonstrated has been a
method for determining the surface loading of organosulfide
functional groups, a spectroscopic technique for establishing
the identity of silica gel immobilized rhodium species, and
an oxidation reaction which can accurately measure catalytic
activities and catalyst lifetimes. Thus, any further
attempts to alter the silica surface may be monitored rather
precisely.
The general supposition that increased site isolation
of the silica gel supported rhodium species is directly
related to increased catalytic activity is supported by the
results obtained using [SG]-SH as the support. Very highly
loaded [SG]-SH samples produce catalytic systems of very low
activity. Further manipulation of the silica gel supports in
order to produce better and/or longer lived site isolation
was greatly desired. It was assumed that the general
deactivation of the supported catalysts was dependent to some
degree upon the aggregation, over time, of rhodium species on
the silica surface. A mechanism could be logically
postulated whereby sulfide bound rhodium species exchange


68
with surface silanol protons and thus migrate along the
surface until aggregation occurs. As a result, a
modification of the silica surface was sought which could
remove this possible path of aggregation. One other goal was
to obtain a method for increasing the loadings of site
isolated species per gram of silica support.
The functionalization of unused surface silanol (-SiOH)
groups with alkylsilane moieties results in an effective
method for achieving the previously stated goals. Chloro-
alJcylsilanes are utilized to produce alkyl groups bound to
the silica surface. The reaction of the alkylchlorosilanes
with the silica surface is identical to the surface reaction
with (3-mercaptopropyl)trimethoxysilane as described in
reactions 1-3. The chloro group here reacts as does the
methoxy group in those reactions, forming HC1 instead of
CH^OH. Chlorotrimethylsilane, chlorotriethylsilane and
chlorotripropylsilane were each used to prepare silica gel
samples, along with the same (3-mercaptopropyl)trimethoxy
silane in each case. Samples prepared with alkyl groups and
the sulfide functionality on the silica surface will be
generally referred to as alkylated [SG]-SH, while those with
only sulfide will be called either non-alkylated [SG]-SH or
merely [SG]-SH. The functionalized silica gels will also be
identified by a ratio of surface sulfur to surface silicon
(S/Si) as described previously (e.g., 1S/10S, 1S/20S). The
alkylated gels will also be referred to by a percent
alkylation which is the percent of all unused surface silicon


69
atoms reacted with chloroalkylsilane assuming complete
reactions. The assumption of complete reaction is generally
supported by elemental analyses for carbon which became
possible at levels of substantial alkylation.
Quantitative analyses for sulfide were also done for
alkylated [SG]-SH samples. The values of mmol S/g [SG] for
these were generally slightly lower than for their
non-alkylated analogs. Again, the values obtained for
sulfide content were used to determine the necessary quantity
of silica gel for catalytic oxidations.
Infrared spectroscopy provided a good deal of
information concerning the properties of the alkylated [SG]
-SH gels. As described earlier, reaction of Rh(CO)_S' BF.
(S' = solvent) with [SG]-SH samples provides species whose
infrared spectra are quite useful. Rhodium species bound to
1S/40S and 1S/20S [SG]-SH gels produce the two band
infrared spectrum indicative of the monomeric supported
complex using both non-alkylated and alkylated [SG]-SH
samples. The IR spectrum which results using 1S/10S
non-alkylated [SG]-SH indicates the presence of primarily
dimeric rhodium complex on the silica surface. This
generally supports the estimation discussed earlier in this
chapter that the silica surface must be on the average about
1S/9S or more dilute in order to produce a system in which
most of the rhodium is site isolated. The alkylated [SG]-SH
gels (e.g., 80% methylated) produce the monomeric rhodium
complex on the surface as indicated by their infrared


70
spectra. The alkyl surface covering allows the formation of
a different surface species than its non-alkylated analog at
identical loadings of metal per gram of silica gel. A
mixture of monomeric and dimeric rhodium complexes is present
on the surface of 80% methylated 1S/5S [SG]-SH, while
primarily the dimer is produced on 80% methylated 1S/2.5S
[SG]-SH. These infrared spectra are shown in Figure 12. It
may then be concluded that the alkyl covering cannot prevent
rhodium dimerization on the silica surface past a certain
level of metal loading on the silica gel.
Catalytic Oxidations Using Alkylated Silica Gels as Solid
Supports
The experimental procedures for conducting catalytic
oxidations using alkylated [SG]-SH supports are identical to
those for the non-alkylated systems described in Section B.2.
Again, the most effective way to present data for these
catalytic oxidations is in the form of graphs of millimoles
of 2-hexanone product versus time as measured in hours.
The oxidations obtained using |SG]-SH with 50% of its
available surface covered with trimethylsilyl group (50%
methylated) as supports for the rhodium and copper
cocatalysts are shown in Figure 13. Not only do these
catalysts demonstrate much greater initial activity in some
cases than their unmodified (non-alkylated) counterparts in
Figure 11, but they are still more active after 24 hours.
The 1S/20S (0.05 mmole S/G[SG]) 50% methylated gel in curve


Figure 12.
Infrared spectra for
(C-Hj-OH) ]BF, using
(AT IS/lOSi 50% Me;
(C) 1S/2.5S 80% Me.
immobilized [Rh(CO) -
[SG]-SH supports witn
(B) 1S/5S 80% Me; and


72
I I 1 I I I
2300 2000 1800
(cm'1)


Figure 13. Oxidations using [SG]-SH supports which have some
portion of the silica surface covered with
trialkylsilyl groups. (A) 1S/40S 50% Me;
(B) 1S/20S 50% Me; (C) 1S/10S 50% Me.


A
B
C
ISAo Si 50% Me
ls/20 Si 50% Me
ls/io Si 50% Me


75
B produces virtually linear 2-hexanone production over 24
hours. Compared to the non-alkylated catalyst curve B of
Figure 11 on almost two-fold increase in product has been
obtained after 24 hours and a very active catalyst remains.
At the end of four hours essentially the same amount of
2-hexanone had been produced by curve B in Figures 11 and 13.
Infrared spectra indicated that in both catalysts the
essential species was monomeric rhodium complex before the
start of catalysis. Thus, alkylation of silica gel in this
instance has greatly enhanced catalyst lifetime.
Comparison of lS/lOSi catalyst systems from curve C of
Figures 11 and 13 reveals that the methylated catalyst is
superior almost from the very start of the oxidation. This
result correlates well with the fact that the non-alkylated
catalyst is composed of rhodium dimer, while the alkylated
one contains monomeric rhodium before reaction. This
demonstrates that higher loadings of catalytically active
complex can be obtained under site isolated conditions by
diluting the functionalized reagent in the hydrocarbon matrix
formed by -Si(CH^)^. A very active catalyst is still present
after 24 hours.
A surprising result is represented by curve A in
Figures 11 and 13. According to infrared spectroscopy site
isolation (rhodium monomer) exists in both systems before
reaction. The diffusion problem described in relation to
Figure 12 has apparently been decreased by the greater
affinity of alkene for the alkylated surface than for


76
solvent. Such a rationalization explains the greater initial
activity of curve A in Figure 13 versus Figure 11 as well as
the increased activity after 24 hours.
Figure 14 shows the results of 1-hexene using catalysts
supported on 50% and 80% ethylated silica gels. They are
generally more active than the non-alkylated gel catalysts
and are still very active after 24 hours. The 1S/10S 80%
ethylated catalyst (curve E) is less active and the 1S/20S
80% ethylated gel (curve D) more active than might have been
predicted. Samples which were 80% methylated yielded results
similar to those of the 50% methylated gels. It is also seen
in Figure 14 that increasing the percent alkylation does not
have a drastic effect on catalytic activity.
The 80% propylated [SG]-SH samples produce catalytic
results very much like those of the non-alkylated silica gels
of Figure 11. Figure 15 displays oxidations run for longer
time periods, each done with 1S/20S [SGj-SH gels which have
different surface modifications. The 80% methylated gel
(curve B) is still active after 140 hours. It can be seen
that the 80% ethylated gel is less active than the methylated
one, while the propylated catalyst is nearly identical to the
non-alkylated sample. The propylated silica gels, and to a
lesser extent the ethylated ones, are markedly slow in
"wetting" by ethanol. Perhaps it is this increased
hydrocarbon-like nature of the surface which accounts for
their decreased efficiency as catalytic supports relative to
the methylated gels. Thus, even though enhanced solubility


Figure 14. Oxidations of 1-hexene using [S
supports. (A) 1S/40S 50% Et;
(C) 1S/10S 50% Et; (D) 1S/20S
(E) 1S/10S 80% Et.
]-SH samples as
B) 1S/20S 50% Et;
80% Et;


mmol 2 hexanone
3.2
2.8 -
2.4
2.0
1.2
0.8 -
04 -
A
B
c
D
E
ISAo Si 50% Et
1 S/20 Si 50%Et
,s/l0 Si 50%Et
ls/20 Si 80%Et
ls/iO Si 80%Et
time, hr
00
O CD


Figure 15. Oxidations of 1-hexene over longer time periods
(A) 1S/20S not alkylated; (B) 1S/20S 80% Me;
(C) IS/2OSi 80% Et; (D) 1S/20S 80% Pr.


CL)
c
o
c
o
X
_c
I
OJ
o
E
E
12.0
10.0 -
8.0 -
6.0
4 0
2.0
60 00
time, hr
A
IS /20 Si
Not Alkylated
B
is/20 Si
80 % Me
C
ls/20 Si
80% Et
D
IS/20 Si
80 % Pr
B
00
o
100
120
140


81
of the alkene in the surface layer may occur, exclusion of
the solvent would inhibit the reaction.
An investigation was undertaken to determine whether
under conditions in which the large amounts of silica gel
used in 1-hexene oxidations when the 1S/40S (0.025 mmol S/g
[SG]) gels are employed as catalyst supports diffusion might
become rate-controlling. A typical 1-hexene oxidation
employing 1S/40S non-alkylated [SGj-SH was run. A second
oxidation using one-half the amount of rhodium and copper,
and thus one-half of the silica gel support, was also run.
All other initial conditions and amounts of reactants were
identical. Assuming that diffusion is not rate-controlling
the rate of this oxidation should have been one-half of the
original rate since the oxidation is first order in rhodium
concentration.*^ Figure 16 clearly shows the reaction with
one-half of the silica gel supported catalyst to have a rate
greater than one-half of the normal oxidation. The dashed
line C is one-half of the curve A. Thus, there seems to be
some reaction inhibition due to the large amounts of silica
gel support used in the 1S/40S oxidations (9-12 g), which is
near the limit of the mass of gel which may be stirred in
this experimental apparatus. This result may be ued to help
explain why in general several 1S/40S (0.025 mmol S/g[SG])
supported catalysts are not as active as their 1S/20S (0.05
mmol S/g [SG ]) counterparts (e.g.,
Figure 11).


Figure 16.
Oxidations of 1-hexene used to investigate
diffusion problems. (A) A "typical" 1-hexene
oxidation using 1S/40S [SG]-SH; (B) oxidation
using one-half of the amounts of 1S/40S [SG]-SH,
rhodium catalyst and copper(II) used in (A);
(C) a representation of one-half of curve A.


time, hr
mmol 2-hexanone
CD
£ 8
SG + RMCO.K + CuOIM /40 Si)


84
Possible Effects of a Different Rhodium Catalyst
Characterization
The design and implementation of the supported
catalytic systems have been based on Mimoun's
characterization of the active catalyst as a rhodium(I)
complex. The possible characterization of the catalyst as a
rhodium(III) species as discussed in Chapter II may have
several implications. Chloride ion may also be quite
important since 3-5 equivalents of chloride ion promote
better homogeneous oxidations using [Rh(CO)2S'nlBF4 (S' =
solvent) and given that the most stable homogeneous catalyst
. 6 4
species may be rhodium chloride complexes of same type.
Chloride ion cannot be added to the [SG]-SH systems without
extensive leaching occurring. The possible use of a
supported multi- dentate ligand for the immobilization of a
rhodium(III) catalyst should be considered for future use.
It would also be of interest to compare the effects of
alkylation of a multidentate ligand silica gel support to
those presented here for a monodentate ligand system.
Conclusions
The spectral properties and catalytic behavior of the
described systems demonstrate that isolating functionalized
lSG]-SH groups with [SGj-SiR^ (where R is alkyl) leads to
some very pronounced changes. The stability of the
methylated catalysts is greatly enhanced over that of the


85
non-alkylated systems. On non-alkylated [SG]-SH it is
possible that the derivatized silanol groups may exchange
with protons on nearby silanol groups and thus migrate along
the surface, aggregate and become inactive. The alkylated
gels remove -OH groups and would be able to effectively
suppress such a process leading to a longer lifetime for
site-isolated conditions. The mixing of reagents prior to
functionalization also ensures a better distribution of
functional groups over the surface under site isolated
conditions and enables one to attain a more concentrated site-
isolated catalyst.
In the specific catalytic system studied, increasing
the length of the alkyl chain covering the silica surface to
ethyl and propyl decreases catalytic activity over the methyl
covering. This may be due to solubility properties as
discussed earlier, or perhaps due to increased efficiency at
keeping the two cocatalysts apart. This approach should
still find general application and utility in the area of
hybrid catalysts where site isolation is a desired feature.


86
Experimental
General Procedures
All solvents and reagents were of reagent grade and
used without further purification unless otherwise specified.
The [Rh(CO)-Cl ]-41 and [Rh(CO)-,S' IbF,62 (S' = solvent) were
2 2 n 4
prepared as reported in the literature or purchased from
Aldrich and recrystallized from n-hexane. The ^CH^O) ^Si (Ci^Ct^-
CH^SH) and ClSiiCH^)^ were obtained from Aldrich and
ClSi(C2H5)2 and CISi ( C^H.^) ^ from Petrarch Systems. Silica
gel was grade 62 from Davison Chemical.
Infrared spectra were recorded on a Perkin-Elmer model
283B infrared spectrometer. The GLC were obtained with a Varan
model 940 FID instrument using a 3m, 1/16 in. i.d. copper
column packed with Chromasorb P supported diethylene
glycoladipate or with a Varian model 3700 FID chromatograph
using an 8 ft, 1/8 in. column of the same material. The
2-ftexanone production was quantified using 2-heptanone as an
internal standard. Electronic absorption spectra were taken
on a Cary 14, and all samples were run in air at ambient
temperatures and pressures.
Preparation of Silica Gel Supports
All reactions of functionalizing silanes with silica
gel were done under argon with xylenes as solvent. Silica
gel was stirred in xylenes under argon, followed by heating,
and then a solution of one or more silanes in xylenes was


87
added dropwise to the hot silica gel slurry. The non-
alkylated [SG]-SH gel was made by adding (CH^O)3Si(CH2CH2~
CH2SH) to the gel. The [SG]-SH alkylated gels were made by
adding a solution of the mercaptosilane mixed with R^SiCl (R=
CH^, C2H5 or ). This technique is preferable to adding
each silane in separate steps. After refluxing 24 hours, the
silica gels were thoroughly washed with xylenes, ethanol and
then dried at ^90C. The silica gels remain white in
appearance.
Determination of -SH on Silica Gel
Silica gel and its surface silanol groups were reacted
with (CH30)3Si(CH2CH2CH2SH) to produce the [SG]-OSi(OCH3)2~
(CH2CH2CH2-SH)(abbreviated as [SG]-SH). R3SiCl (R=methyl,
ethyl or propyl) was used to complete reaction of the silanol
groups and cover the silica gel surface with alkyl groups.
Evidence that trialkylsilyl groups are bound to the surface
is obtained by a substantial increase in the percent carbon
found in the elemental analyses and by an increase in the
lifetime of the functionalized catalyst.
Electronic absorption was used to determine the amount
of sulfide on each silica gel sample ( [SG]-SH). The [SG]-SH
samples were stirred with freshly prepared [Rh(CO)2S' ]BF4
(S' = solvent), the solid filtered off and the electronic
absorption spectrum of the filtrate taken. From a
calibration curve of the rhodium complex concentration versus
its absorbance at 390 nm the amount of rhodium in the
filtrate is measured. The amount of rhodium on the gel is


88
determined by the difference of the known initial amount of
rhodium and the amount of rhodium in the filtrate. Assuming
complete reaction of one rhodium per sulfide, the amount of
rhodium is equal to the amount of sulfide on the silica
surface. An analysis of this type was done for all samples.
Samples were prepared which varied in surface sulfide
concentration and in percent of available surface silanol
groups which were "alkylated" (reacted with trialkylchloro-
silane). Assuming tetrahedral coordination around silicon
and oxygen atoms with an approximate silicon-oxygen bond
distance of two Angstroms, and assuming that as an upper
limit a flat surface exists with all surface groups being
O
silanols, a separation of 6.5 A exists between the oxygens of
surface hydroxyl groups. This corresponds to one surface
-19 2
hydroxyl per 4.3 x 10 m of surface so it can be
calculated that as an upper limit there are about one mmol
surface silanol group atoms per gram [SG]. With this value
it can be determined that the [SG]-SH samples prepared
contain approximately 1/40, 1/20, 1/10 and 1/5 millimoles
sulfide/millimole surface Si (S/Si) which corresponds to
0.025, 0.05, 0.10, 0.20 and 0.40 mmol S/g[SG]. Silica gel
samples used as catalytic supports will be referred to by a
(S/Si) ratio and by a number of mmole S/g[SG]. In some
instances the percent alkylation (methylation, ethylation or
propylation) of the surface silicon sites will also be used.


89
Catalytic Oxidations of 1-Hexene
All catalytic 1-hexene oxidations were run in 250 mL
Parr pressure bottles equipped with brass Swagelok pressure
heads. These were constructed to allow purging with 0^, as
well as sampling of the solution under reaction conditions
during the course of the reactions. The 2-hexanone
production was measured by GLC.
All catalytic reactions were run using 0.074 mmol
[Rh(CO)2S'n]BF4 (prepared as reported earlier and used
immediately) and 0.0179 g Cu(NO^)23H20 (0.074 mmol). The
amount of silica gel employed was varied to provide enough
-SH sites to bind ail of the rhodium and copper with a 10%
excess (e.g., 4.9 g of 1S/20S 80% Et [SG]-SH). Both metal
ions are attached to the [SG]-SH samples through the -SH
moiety producing a lemon-yellow to yellow-green supported
catalyst. The catalyst was added to a 250 mL Parr bottle
along with 0.32 mL 0.47 M HC104 (0.150 mmol, as an ethanol
solution prepared from aqueous cone. HC104), 1.136 mmol
2-heptanone, 45 mL absolute ethanol, and 15 mL 1-hexene
(purged through alumina to remove peroxides). This mixture
was purged 5 times with 60 psi 02, set to 40 psi 02, and the
reaction initiated by placing the system in a 70C oil bath.


CHAPTER IV
THE SYNTHESIS AND CATALYTIC APPLICATIONS
OF A MULTIDENTATE LIGAND AND CORRESPONDING METAL COMPLEXES
BOUND TO SILICA GEL
Introduction
The use of a polymer as a support for catalysts was
discussed in Chapter III for a specific system which employed
a monodentate chelate on silica gel. The general use of
polymers as supports for catalysts and chelates, and also as
synthetic reagents, has developed enormously since their use
in peptide synthesis was shown by Merrifield approximately
twenty years ago.^^ It was generally assumed for several
years that there was little, if any, interaction between
functionalized sites on resins such as polystyrene. This is
now known not to be the case, and Chapter III demonstrated
some of the rather stringent conditions which must be met in
order to achieve site isolation on a support such as silica
gel.
90


91
Another general approach to preparing stable polymer
bound metal complexes is that of first attaching a
multidentate ligand system to a polymer backbone and then
adding the metal ion to the previously formed ligand. There
have been many reports discussing polymers which contain
chelating groups of various sizes and donor atoms.An
excellent review of this area is cited here as reference 70.
Most of the polymer bound chelates studied are mono- or
bidentate, with only a few tri- and tetradentate systems
having been investigated.^^ Resins with bidentate
chelate groups often must provide a metal ion with two or
three chelating groups since many metal ions prefer forming
four or six coordinate complexes. This led to the common use
of uncrosslinked or lightly crosslinked polymers. The
ambiguity involved in trying to characterize these polymer
bound metal complexes makes it very difficult to interpret
data from catalytic reactions or physical methods.
In virtually all of the literature reports cited in
this area, there is no attempt made to isolate functionalized
sites from one another and in many cases two or more sites
must interact in order to provide successful chelation.
Chapter III discussed in detail the conditions required
to achieve site isolation on silica gel and surface
modifications which may enhance that isolation. The initial
sections of this chapter will discuss the preparation of a
stable multidentate ligand site isolated on silica gel which
can complex a variety of metal ions into polymer bound


92
complexes of a known geometry. Investigations of several
applications of these polymer bound complexes will then be
presented, followed by investigations into the use of
different solid matrices as chelate metal complex supports.
The ligand prepared on silica gel is a pentadentate
ligand which complexes several different metal ions. The
silica gel supported complex of iron(III) was used to
investigate some known homogeneous reactions.
Biological oxidation processes are generally quite
selective and sensitive and as a result attract the attention
7 2
of many chemists. Cytochrome P-450 is one enzymatic system
which can catalyze several types of oxidative
transformations, including selective alkane hydroxylations
and has therefore been an object of much research effort.
Several studies have proposed intermediate high-valent
oxometalloporphyrin species in the catalytic cycles of
7 3 7 4
several heme-containing oxygenase enzymes. Simple
chemical models for cytochrome P-450 were sought in order to
provide insight into some of the basic processes involved in
its chemical reactivity. A significant finding was the
realization that iron,75 chromium,76 and manganese77
porphyrins could catalyze oxygen transfer from iodosylbenzene
7 8
to simple hydrocarbons. In all of these cases, a metal-oxo
species is proposed as an intermediate, although complete
mechanistic details have not been determined. However, it
was the possibility of generating silica gel supported iron
or manganese oxo species to achieve some type of oxidative


Full Text

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MECHANISTIC AND SITE ISOLATION STUDIES
OF TRANSITION METAL OXIDATION CATALYSTS
By
DAVID CHAPPEL PRIBICH
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN
PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1985

To Susan, Jean, Mitch and Pat Pribich

TABLE OF CONTENTS
PAGE
ABSTRACT v
CHAPTER
IGENERAL INTRODUCTION 1
IITHE SPECIFIC OXIDATION OF [Rh(CO)-Cl], BY
0, VIA THE COORDINATION OF IN SITO GENERATED
HYDROGEN PEROXIDE 3
Introduction 3
Background 5
Results and Discussion 8
Characterization of the Catalyst
as a Rhodium(III) Chloride Complex .... 8
Mechanism of the 0- Oxidation of
[Rh(CO)_C1 ] - to Rhodium(III)
Chloride 19
Conclusion 43
Experimental Section 44
Catalytic Oxidation of 1-Hexene 45
Preparation of RhCl, (H-,0) -CH--
CH OH (II) 46
Determination of Acetone Production. ... 46
Titration of [Rh(C0)-Cl]- with
HOOH 47
IIIENHANCED SITE ISOLATION ON SILICA GEL AND
IMPROVED LIFETIMES OF SITE ISOLATED CATALYSTS . 49
Introduction 49
Results and Discussion
Polymer Support of the Catalyst 80
Catalytic Oxidations of 1-Hexene by
Supported Complexes 59
Alkyl Covering of the Silica
Surface to Improve Site Isolation
and Catalysis 6 '
Catalytic Oxidations Using Alkylated
Silica Gels as Solid Supports ; 9
Possible Effects of a Different
Rhodium Catalyst Characterization .... 84
Conclusions 84
i i i

Experimental 86
General Procedures 86
Preparation of Silica Gel Supports .... 86
Determination of -SH on Silica Gel .... 87
Catalytic Oxidations of 1-Hexene 89
IV THE SYNTHESIS AND CATALYTIC APPLICATIONS OF A
MULTIDENTATE LIGAND AND CORRESPONDING METAL
COMPLEXES BOUND TO SILICA GEL 90
Introduction 91
Results and Discussion 94
Synthesis of a Salen Ligand on
Silica Gel 94
Oxygen Transfer Using [SG ]-Fe(III)-
SalDPT and [SG ]-Mn (11) Sal DPT 101
Synthesis of [SG ]-Fe(II)SalDPT 107
Incorporation of an Active Metal
into a Functionalized Support 110
Synthesis of a Silica Gel Anion
Exchange Resin 117
Titanium Carmde as a Solid
Support 118
Fenton Chemistry 127
Experimental 128
Silica Gel 128
Functionalization of Silica Gel
with l-tnmethoxysilyl-2-( p,m,-
chloromethylphenylethane) 129
Preparation of Silica Gel Bound
3,3 '-Immodipropionitnle 129
Preparation of Silica Gel Bound
bis-(3-aminopropy1)amine [SGj-DPT .... 130
Condensation of Salicylaldehyde with
[SG]-DPT 131
Incorporation of Metal Ions into
[SG ]-SalDPT 132
Incorporation of Fe(II) into [ SG] —
SalDPT 132
Incorporation of Cu(II) into the
Silica Gel Matrix 133
Preparation of Silica Gel Anion
Exchange Resins I34
Titanium Carbide as a Solid
Support I35
Fenton Chemistry H"7
V GENERAL CONCLUSION I38
REFERENCES 139
BIOGRAPHICAL SKETCH 145
iv

Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
MECHANISTIC AND SITE ISOLATION STUDIES
OF TRANSITION METAL OXIDATION CATALYSTS
By
David Chappel Pribich
May, 1985
Chairman: Russell S. Drago
Major Department: Chemistry
Mechanistic work reported here involves the investi¬
gation of the oxidation of 1-hexene to 2-hexanone catalyzed
by Rh(III)/Cu(II) mixtures. A number of results are obtained
that indicate that [RhtCO^Cl^ as a catalyst precursor must
be converted to a rhodium(III) complex before catalysis
occurs. The oxidation of the rhodium(I) precursor to the
active rhodium(III) catalyst in the absence of copper is
reported in detail. An unusual mechanism results which
involves the in situ production of hydrogen peroxide from the
alcohol solvent reduction of 0^. The hydrogen peroxide then
oxidizes [Rh(CO)2ClJ2 to an unstable [Rh(CO)(00H)(?)]
v

intermediate. This oxidation occurs only in solvents
capable of reducing 0-, .
Cofunctionalization of silica gel with trialkylchloro-
silanes and (CH^O)^SiCH^CH^CH^SRh(CO)^ produces a catalyst
for the oxidation of 1-hexene that can be compared with a
catalyst that does not have an R^Si- covering. Physical
methods are used to determine the concentration of groups on
the silica surface and also to determine the loading at
which site separation occurs. The alkylated supports can be
loaded with a greater concentration of the site-isolated
rhodium complex producing catalysts which have greater
activity per gram of catalyst and longer lifetimes than the
corresponding catalysts produced with non-alkylated silica
gels. Increasing the length of the alkyl group used to cover
the surface decreases the effectiveness of the silica as a
catalytic support and eventually leads to a catalyst surface
that is not wetted by ethanol solvent.
A three nitrogen, two oxygen salen-type ligand was
successfully synthesized on silica gel. Cobalt, copper,
manganese and iron metal ions were incorporated into the
supported ligand system. The iron(III) and manganese(11)
systems achieved oxygen atom transfer from iodosylbenzene to
a cyclohexene substrate producing different product ratios
than homogeneous tetraphenylporphyrinato metal systems have
yielded and are also the first supported systems to
achieve this process.
vi

Several other results are reported, including the
preparation of an air sensitive iron(II) silica gel bound
complex, incorporation of copper into the silica gel matrix,
preparation of a silica gel based anion exchange resin, and
examination of titanium carbide as a catalytic support.
Vll

CHAPTER I
GENERAL INTRODUCTION
The efficient conversion of ubiquitous substances on
this planet into other useful species is a desirable and
perhaps even honorable goal which correspondingly attracts
the efforts of large segments of the scientific community.
Specifically, a subset of this broad area is the efficient
catalytic use of naturally occurring dioxygen via interaction
with transition metal centers. The following chapters will
describe investigations which in some way involve this area
of research. A rather detailed study on the formation and
nature of a specific homogeneous rhodium oxidation catalyst
is presented in the second chapter.
The general interest in the Chapter II catalyst led to
work which supported the catalytic system on an inorganic
polymeric solid. Subsequent efforts to maximize the
efficiency of this supported system while gaining detailed
information on the support medium itself are represented in
the third chapter.
1

2
A general broadening of study to include different
metals, ligands, substrates and even solid supports led to
further research; the various results of which are detailed
in the fourth chapter.
Specific background information and introduction is
included with each topic as it is discussed. The general
introduction provided by this brief overview should then
allow comprehension of the pattern of research on
interrelated topics presented in the following.

CHAPTER II
THE SPECIFIC OXIDATION OF [Rh(CO)~C1]_
BY 0- VIA THE COORDINATION OF IN "SITU2
GENERATED HYDROGEN PEROXIDE
Introduction
Homogeneous catalysis has developed rapidly during the
last twenty years as organometallic chemistry has been firmly
established as a major discipline within inorganic chemistry.
The search for new and more efficient catalysts was
intensified as the finite nature of the crude oil supplies
which provide the feedstocks of many important chemical
processes was more closely realized. Oxidations have
specifically received much attention; there have been
estimates that an oxidation step is involved in the
production of over 50% of the chemicals manufactured
industrially. â– *â–  Water, alky lperoxides and dioxygen are
frequently used as oxidation reagents. Dioxygen is the most
desirable one, not only due to its obvious availability, but
also because of its favorable energetics.
3

4
Homolytic and heterolytic are the two major categories
into which metal catalyzed homogeneous oxidations have most
2 3
often been divided. ' Homolytic oxidations are those in
which radical intermediates are produced during the oxidation
process. However, the drawback of most radical processes is
a lack of product selectivity, and that is also a major
problem in these oxidations. One reason for this lack of
specificity is that in many homogeneous metal catalyzed
oxidations of hydrocarbon by 0^ the metals are involved in
4-9
just the first step of reaction. These metals decompose
peroxides and thus initiate free-radical autoxidations.
These free radicals then react with substrates such as
olefins leading to the formation of several products.
Heterolytic oxidations, also known as nonfree-radical
oxidations, involve binding of a substrate to a metal center,
rearrangement, and later release of products. The Pd/Cu
catalyzed oxidation of ethylene to acetaldehyde in the
presence of water^ (the Wacker process) is one well-studied
example. The systems which undergo this type of oxidation
have been the focus of much research aimed at adjusting the
metal centers in order to improve catalytic activity. This
has been especially true since the discovery of Vaska's
complex, Ir(P(CgH^)^)2(CO)Cl, and the realization that it is
able to reversibly bind dioxygen.^ This "oxygen-atom
transfer process" does not involve free radicals and results
in product specificity. Since Vaska's complex was discovered
several 0^ oxidations of non-organic substrates have been

5
12-19
judged to occur by the O-atom transfer process. General
knowledge of this type of reaction is largely dependent upon
the ability to procure detailed mechanistic information. A
mechanistic investigation of one reaction will be presented
in the following sections.
Background
Considering specifically rhodium catalyzed oxidations
of hydrocarbons by dioxygen, several examples have been
reported which seemingly do not proceed by either free
2 o _ 2 4
radical or simple Wacker processes. One of these is
the rhodium/copper co-catalyzed oxidation of terminal olefins
20
to 2-ketones with >98% specificity (reaction 1).
2CH2=CHR + 02 - 2CH 3C(O)R (1)
The Wacker-Smidt process refers to the palladium(II)/-
copper(II) co-catalyzed oxidation of olefins to ketones and
2 s_2 6
aldehydes using water as the direct oxidant.
Palladium(O) is produced as an intermediate in this process,
and the copper(II) is necessary to oxidize it back to Pd(II),
the active catalyst. Only a stoichiometric reaction occurs
and Pd(0) metal is produced if no Cu(II) is used. The
general steps of the mechanism and the net reaction are shown

6
below (reactions 2-5) for the catalytic oxidation of ethylene
to acetaldehyde.
Pd(II) + H20 +
ch2=ch2
+ Pd(0) + H3CCHO + 2H+
(2)
Pd(0) + 2Cu(II)
- Pd(II) + 2Cu(I)
(3)
2Cu(I) + 1/2 02
+ 2H+
- 2 Cu(II) + H20
(4 )
Net: CH2=CH2 +
1/2 02
- CH3CHO
(5)
Water is the direct oxidant here, even though C>2 is consumed.
Dioxygen is reduced to by Cu(I), which reforms the Cu(II)
necessary for oxidizing Pd(0) to Pd(II). Other processes
which are thought to proceed in a similar manner are referred
to as having a "Wacker" mechanism.
Mimoun and co-workers put forth great effort to rule
out a Wacker-type mechanism for reaction 1. Several
experimental observations could not be rationalized by a
20
Wacker mechanism. Thus, despite apparent similarities
between Mimoun's system and the earlier rhodium/copper
catalyzed system which is reported to have a Wacker-type
27
mechanism, the differences are great enough to rule out the
hydrolysis process found in Wacker chemistry for Mimoun's
system.
Mimoun proposed that the catalyst in the Rh(III)/Cu(II)
oxidation system is a rhodium(I) complex produced from the
ethanol reduction of RhCl^ and Cu(II) in the initiation step
shown in reaction 6.

7
RhCl3 + 2CH2=CHR + Cu(C104)2 + 1.5CH3CH2OH ^
[Rh(CH2=CHR)2]C104 + CuCl(s) + HC104 + 2HC1 +
1.5 CH3CHO (6)
The observations which lead to this proposal by Mimoun
are the following: (1) active catalysts are formed by using
[Rh(CgH14)2C1]2 in the presence of 2 equivalents of HC1
instead of RhCl3 *31120; (2) an amount of acetaldehyde
approximately equal to the moles of catalyst used is produced
from ethanol oxidation at the beginning of the catalytic
reaction; and (3) 85% of the Cu(II) precipitates as CuCl at
the beginning of the catalytic 1-hexene oxidation.
Initiation of the catalysts would then be possible by the
binding of dioxygen to the reduced rhodium species. From
reaction 6 it can be seen that there are at least two
possible needs for an equivalent of Cu(II) to produce the
best catalytic conditions. The copper(II) is either
necessary for the reduction of RhCl3*3H20 to Rh(I) with the
stoichiometric production of CuCl, or for the removal of
chloride ion from solution to yield a more unsaturated
rhodium center. A combination of both roles for copper is
possible, and Mimoun did not eliminate some other possible
need for copper.
The mechanism Mimoun proposed involves a metal centered
oxygen atom transfer involving coordination of dioxygen and

8
olefin to the rhodium(I) cation from reaction 6, a
rearrangement to a peroxometallocycle, and then a decom¬
position to the rhodium(I) complex and the oxidation
products. Figure 1 shows this mechanism. It was based upon
Mimoun's suggestion that the active catalyst was a rhodium(I)
complex that led to the preparation of a silica gel organo-
sulfide supported rhodium(I) complex. This heterogenized
complex produced an active and stable catalyst for the
2 8
oxidation of 1-hexene to 2-hexanone (vide infra, Chapter
III) .
Results and Discussion
Characterization of the Catalyst as a Rhodium(III) Chloride
Complex
The rhodium carbonyl dimer (A), [Rh(CO)2C1 ] ^, was
selected as the catalyst precursor due to the facile loss of
the CO ligands in the presence of 0^, the presumed need for a
rhodium(I) catalyst to coordinate 0^ and olefin, and the
usefulness of the CO ligands for infrared analyses.
Employing A as a homogeneous catalyst for reaction 1 at
various chloride concentrations and in the presence of Cu(II)
at 70°C, the data in Figure 2 were obtained. Note that the
maximum initial 1-hexene oxidation rate (indicated by the
amount of 2-hexanone produced) is achieved using a
chloride/rhodium mole ration of 3:1, as was originally

Figure 1.
The mechanism proposed
for the Rh(III)/Cu(II)
oxidation of 1-hexene
by Mimoun to account
catalyzed 0~
to 2-hexanone.

10
RhCl»

Figure 2.
Effect of increasing the chloride/rhodium
ratio on the initial rates and catalyst
stabilities for the C>2 oxidation of 1-hexene
at 70 C and 52 psi 0^7 in the presence of one
equivalent of Cu(II)7

mmole 2-he xa none
£k CD ro ^
ZT
EFFECT

13
reported for this system at 40°C. However, increasing the
chloride/rhodium ratio to 5:1 at 70°C causes a considerable
increase in catalyst stability with little change in the
initial rates, in contrast to the result obtained at 40°C,
where a large drop in activity was found for the 5:1 ratio.
(For example, after 20 h at 70°C with a 3:1 Cl/Rh mole ratio,
the catalytic activity is only 7.5% of the initial value,
while after the same time period with a 5:1 Cl/Rh ratio the
activity is 34% the initial rate.) Increasing the
chloride/rhodium ratio to 10 causes an even further increase
in catalyst stability at 70°C (the activity after 20 h is 51%
of the initial rate). A similar beneficial effect of
increasing the Cl:Rh ratio to 5:1 was observed in analogous
experiments with Cu(II) absent. This suggests that a
specific interaction of chloride with rhodium and not copper
leads to catalyst improvement. Furthermore, the marked
dependences of both initial rate and catalyst stability on
such large chloride concentrations suggest a rhodium(III)-
chloride interaction. These results, along with others to be
presented, indicate that a rhodium(III) chloride complex is
the catalyst or the immediate precursor.
Experiments were conducted investigating the effect of
dioxygen pressure on 1-hexene oxidation at 70°C. The use of
[Rh(CO)2C1 12/ H2S04 and NaC1 to catalyze the production of
2-hexanone from 1-hexene can be accomplished in the absence
of Cu(II). These results, along with the existence of an
induction period, are shown in Figure 3. Also demonstrated

Figure 3.
Demonstration of the dependence of the length
of the induction period on the pressure of
02, in the absence of Cu(II) at 70 C,
using [RhiCOJ^Cl]- as the precursor. The 02
pressures are ror A, 3.7 atm; B, 1.9 atm; C7
1.4 atm; and D, 1.0 atm.

15
c
o
2 0
hours
”i—
120

16
is the first-order dependence of the induction period on
dioxygen pressure. During the induction period the solution
color changes from light yellow (the color of [Rh(CO)^C1]2 >
to bright orange (normal for rhodium(III) chloride
29
complexes). No induction period is seen when RhCl^’3H20
is used rather than A, nor when 0.1 equivalent or more of
Cu(II) is added to the reaction mixture. A proposal
suggested by these experiments is that of the dioxygen
oxidation of [Rh(CO)2Cl]2 to a rhodium(III) chloride complex
(which is either the active catalyst or an immediate
precursor) during the induction period.
Further investigation of this system involved the
reaction of A, dioxygen, and HC1 in ethanol, at 40°C in the
absence of 1-hexene substrate. A bright orange complex (C)
was isolated as RhCl^(H^O)2’CH^CH^OH after 12 hours of
reaction. This process is described by reaction 7.
[Rh(CO)2 C1]2 + 4HC1 + 202 + 4CH3CH2OH -
2RhCl3(H20)2*CH3CH2OH + 2CH3CHO + 4CO (7)
The rhodium product (C) was characterized by elemental
analysis, molecular weight determination, and its infrared
and visible spectra. ^ The stoichiometry for reaction 7 was
verified in both [Rh(CO)2Cl]2 and HC1, but this was not
possible for C>2, CH3CH2OH, and CINCHO due to the catalysis of
reaction 8 by C (vide infra). The addition of an equivalent

17
2CH3CHROH + 02 -*â–  2CH3CRO + 2H20 (8)
R = CH3 or H
of Cu(II) or the use of [Rh ( CgH^ ) 2C1 ] 2 as the rhodium(I)
precursor considerably speeds up reaction 7 (vide infra) but
does not affect its outcome. Compound C catalyzes the
oxidation of 1-hexene to 2-hexanone as efficiently as
RhCl3'3H20 and without the occurrence of the induction period
observed when using [Rh(CO)2Cl]2 as the catalyst precursor
under identical conditions (see Figure 3). The observed
solution color changes and other results described above
indicate that under reaction conditions for the catalytic
oxidation of 1-hexene (reaction 1), the rhodium(III) complex
(C) is produced from the oxidation of [Rh(CO)2C1]2. An
explanation for the role of copper(II) and a more detailed
study of reaction 7 will be discussed in the second part of
this chapter.
To rule out the possibility that RhClg-3H20 (or C) may
be subsequently reduced to a rhodium(I) complex by alcohol
solvent to initiate catalysis (as proposed by Mimoun in
reaction 6), we investigated the initiation step using
RhCl3*3H20 and Cu(N03)2 -2.5H20 as precursors. For our study
we chose isopropyl alcohol as solvent since upon oxidation
this alcohol forms acetone which is much easier to
quantitatively measure than the more volatile acetaldehyde
(produced from ethanol). Using GLC, we found that in the

18
presence of 1 equivalent of Cu(II) only 0.5 equivalents of
acetone is produced immediately on mixing all reagents
necessary for the catalytic oxidation of 1-hexene and that
its concentration remains constant for at least 0.5 h. From
this result we can rule out the simultaneous reduction of
Rh(III) and Cu(II) proposed in reaction 6 because this would
require the oxidation of 1.5 equivalents of isopropyl
alcohol. We propose that reaction 9 initiates the catalytic
cycle for this system
Cl" + Cu2+ + 0.5(CH3)2CHOH
1 atm C>2 at 40°C
isopropyl alcohol
1-hexene
CuCl. , + 0.5 (CH-,) „C0 + H +
( s ) 3 2
(9)
when RhCl3*3H20 is used as the catalyst precursor. Our
proposal requires that only enough reducing equivalents are
2 +
provided by isopropyl alcohol for the reduction of Cu to
form CuCl. Copper(I) chloride may be isolated from the
reaction mixture in 85% yield without affecting the catalytic
oxidation.

19
Mechanism of the 0-, Oxidation of [Rh(CO)„C1K to Rhodium(III)
Chloride
The oxidation of [Rh(CO)2Cl]2 (A) to rhodium(III)
trichloride (C) by 02 was originally studied because of our
interest in characterizing the active catalyst for the
Rh/Cu-co-catalyzed 1-hexene oxidation (reaction 1).
Copper(II) was excluded in these initial investigations to
facilitate the interpretation of the electronic absorption
spectra, elemental analysis and molecular weight data. The
substrate 1-hexene was excluded from these solutions to avoid
its catalytic oxidation to 2-hexanone after the formation of
the rhodium(III) chloride product. As described in the
previous section, the exclusion of Cu(II) and 1-hexene during
these studies proved to be quite useful for characterizing
the rhodium catalyst. The oxidation of [Rh(CO)2Cl]2 to
rhodium(III) chloride was generally monitored by electronic
absorption spectroscopy in order to determine the reaction's
end point. In the course of these studies it was found that
at elevated 02 pressures (3-5 atm) an unusual intermediate
exhibiting a visible absorption band at 385 nm could be
detected. This observation led to a detailed investigation
of the mechanism of the C>2 oxidation of [Rh(CO)2Cl]2 to
rhodium(III) chloride in reaction 7, and the results are
presented below.
The electronic spectral changes accompanying the
oxidation of the [Rh(CO)2Cl]2 (A) to rhodium(III) chloride
(C) in the absence of both Cu(II) and 1-hexene is shown in

20
Figure 4 as a series of spectra recorded over the course of
the reaction. The growth and decay of an intermediate (B)
with an absorbance at 385 nm is noted. The charge-transfer
band beginning at the shortest wavelength is a result of A,
while the band at 480 nm is produced by C. As shown in
Figure 5, intermediate B is more stable in the presence of
excess Bronsted acid (8HC104/A). The presence of two
isosbestic points (at 377 and 435 nm) in both Figures 4 and 5
suggests the formation and subsequent reactivity of only one
intermediate. The isosbestic point at 377 nm is a result of
the reaction of A to form B at the beginning of reaction 7
(before much final product C has been formed). Early in the
reaction the decomposition of B to C becomes quite
pronounced, and this point disappears. The second isosbestic
point emerges at 435 nm when all A has been consumed and
results from the exclusive reaction of B to form C.
The initial rate of formation of B was found by visible
spectroscopy to follow the rate expression shown in eq. 10,
k[H+][02]
(10)
which is independent of the concentration of A. The
zero-order dependence on [A] rules out a mechanism involving
initially the formation of a rhodium hydride followed by the
insertion of dioxygen to form a rhodium hydroperoxide
intermediate, which occurs with [RhH(CN)4(H20)],
31e
and is

Figure 4. Series of visible spectra resulting from the
02 oxidation of [Rh(CO)2Cl]2 at 40°C in the
absence of any HC1CK. Initial Rh(C0)2Cl 2
is 0.98 x 10 M. Spectra were recorded over
a 12 hour period.

absorbance

Series of visible spectra resulting from the
C>2 oxidation of [RhiCOJ^ClL at 40 C in the
presence of 8 equivalents HC10., but other¬
wise same conditions as used for data
presented in Figure 4.
Figure 5.

absorbance
K>
-P*.

25
32
proposed in two other studies. The rate law in eq. 10 is
surprising because it indicates that the initial step or
steps in reaction 7 (those including and preceding the
rate-determining step) involve a reaction between H+, 0^, and
possibly CH^CI^OH, forming an intermediate oxidant which
subsequently reacts with [Rh(CO)2CI]2•
We investigated the possibility that peroxide could
play the role of direct oxidant in reaction 7. This was
confirmed by experiments involving the titration of A with
HOOH to form C in the absence of dioxygen, monitored by
visible spectroscopy (reaction 11, in which S' is solvent).
[Rh ( CO) 2C1 ] 2 + 4HC1 + 2H00H + S' -*â– 
2RhCl3(H20)2’S' + 4CO * (11)
Because HOOH slowly disproportionates or is reduced in
ethanol, as well as being consumed in a competing side
reaction (vide infra), the oxidation of A to C in this
solvent goes to only 70% completion. Very significantly the
oxidation of A by HOOH proceeds with the formation of the
same intermediate [B] as produced with 02 as oxidant,
indicating that reaction 11 and reaction 7 occur through
similar mechanisms. The kinetic rate law for reaction 11 was
determined by using Fourier transform infrared spectroscopy
(FT-IR) to monitor the consumption of A, and is shown in
equation 12. Several reports describe the reaction between a

26
-d[A]/dt = k([Rh(CO)2C1]2)[HOOH] (12)
metal complex and peroxide to form a coordination
compound. ^ The reaction in eq. 11 proceeding as
described above would exhibit the rate law shown in eq. 12.
On the basis of these arguments and those that follow, we
propose that intermediate B results from the coordination of
HOOH to ÍRh(CO)^C1]2• A proton NMR analysis at -70°C showed
no evidence for B possessing a hydride ligand. Any hydride
species generated from the oxidative addition of HOOH to A
apparently are acidic, and fast exchange of all protons with
the alcohol solvent is very likely occurring.
The characterization of B was assisted by an FT-IR
spectroscopic study of reaction 11. Immediately on adding
HOOH to a solution of A and HC1 in ethanol, the formation of
a complex exhibiting a CO stretching band at 2102 cm ^ is
observed, and this band increases in intensity at the expense
of the bands due to A (at 1995 and 2069 cm ^; Figure 6). The
growth and subsequent decay of the CO band at 2102 cm ^ was
found to correlate directly with the band due to B at 385.nm
observed in the electronic absorption spectra. Therefore,
intermediate B retains one CO ligand. The assignment of the
band at 2102 cm ^ to coordinated CO was confirmed by use of
â– ^CO in the experiment.
That B is a hydroperoxo rather than a u-peroxo complex
is evidenced by our ability to substitute tert-butyl
hydroperoxide (t-BuOOH) for HOOH in reaction 11 to obtain a

Figure 6
Series of infrared spectra obtained from the
HOOH oxidation of [Rh(CO)2Cl]2 in ethanol.
(A) Spectrum of [Rh(CO)-,CI] Reaction was
Spectrum lhu^u/.
run using 0.84 x 10 M¿[RhfCO)_Cl] 2.
Spectra were recorded at (B) 0.25 hours
0.55 hours; and (D) 1.83 hours.
(C)

28

29
much slower reaction and the formation of an intermediate
analogous to B with an electronic absorption band at about
385 nm^ and an infrared CO stretch at 2099 cm ^, 3 cm ^
lower than that found for B with HOOH. Since t-BuOOH is not
known to bridge two rhodium species in the y-peroxo
configuration, we suggest that B is not a y-peroxo complex.
Only a limited number of stable hydroperoxide and alkyl
peroxide complexes of the platinum metals have been reported5
(not including those with Schiff base or bio-type ligands),
and some of these are capable of oxidizing terminal olefins
3 X ^ b
to 2-ketones. ' Intermediate B is only formed in the
presence of HC1 and is not formed on substituting either
HC104 or N(C2H<- ) 4C1 *H20 for HC1. Thus, both a proton and an
additional chloride are required in the formation of the
intermediate. We propose that intermediate B is
H2 [Rh(CO)Cl2- (OOH)], produced as shown in eq. 13. Use of
the oxidation
[Rh(CO)2Cl]2 + 2HOOH + 2HC1
2H2[Rh(CO)Cl2(OOH) ] + 2CO (13)
state formalism to describe these species is potentially
misleading. An oxidative addition of HOOH to a Rh(I) complex
produces HRhIIIOOH. Deprotonation generates Rh^OOH . After
a number of attempts, we have not been able to observe the
0-0 stretch between 800 and 900 cm 1 expected for a
coordinated peroxo group in the infrared spectrum. This is

30
due to the low concentrations necessary to stabilize this
intermediate, the poor window in this region of the infrared
spectrum for ethanol solvent, and the hydrogen bonding in
this system which would broaden this band. When the
intermediate is generated with 0^ and excess 0, is removed, it
spontaneously decomposes to rhodium(III) chloride over
several hours. This is consistent with the formulation of
this intermediate as [Rh(CO)Cl^(00H)], for this species
possesses two oxidizing equivalents in the peroxo (or
hydroperoxo) ligand.
Intermediate B is not formed in the absence of HC1 in
reaction 11, but the reaction in eq. 14 occurs under argon in
ethanol solvent,
Ar
[Rh (CO) 2 C1 ] 2 + HOOH - 2C02 + D (14)
producing free CO^ from the oxidation of a CO ligand and a
very deep brown rhodium(I) complex (D) exhibiting a broad CO
stretching band at 2048 cm Thus, [Rh(CO)2Cl]2 could be
reformed from D by exposure to a CO atmosphere, and the
production of C02 from the CO oxidation by HOOH is catalytic
in A in a CO atmosphere. This reaction has been previously
3 4
reported in benzene, where D precipitates. It is
3 4
reported that redissolving this solid in ethanol and
exposing it to CO leads to the formation of a rhodium(I)
carbonyl complex with a spectrum similar to A. Reforming
[Rh(CO)2Cl]2 from D under CO is significant because it

31
indicates that D is a rhodium(I) complex and that the
irreversible oxidation of rhodium(I) to rhodium(III) by HOOH
in ethanol is slow relative to the oxidation of the CO
ligands to C02 (which takes several hours). These results
further suggest that in the presence of HC1 the reaction
between A and HOOH produces the relatively stable rhodium(I)
hydroperoxo coordination complex B as an intermediate. In
the presence of HC1 reaction 3 is faster than reaction 14,
and the majority of HOOH is consumed to form B rather than
C02 and D. That reaction 14 does occur to a small extent in
the presence of HC1 can be seen in Figure 6, in which the
band at 2334 cm ^ due to C02 is evident. This competing
reaction accounts, at least in part, for the incompleteness
noted for the titration of A with HOOH in reaction 11.
The stabilization of B by excess Bronsted acid,
evidenced by a comparison of the electronic absorption
spectra in Figures 3 and 4, can be explained by considering
the deprotonation of the RhOOH group as the initiation step
for the reaction of B to form C. A further investigation of
the decomposition characteristics of B also proved to be
useful. Upon isolation of a mixture of B and C by quick
evaporation of a dilute solution to dryness under vacuum, B
decomposes within a minute to a wet solid. An infrared
spectrum of this product revealed a large concentration of
water in addition to a high-energy CO stretching band at
2132 cm 1 (shifted from 2102 cm 1 for B). These are the
results expected from the fast, autocatalytic decomposition

32
of a hydroperoxo complex. The reduction of the hydroperoxo
ligand by Rh(I) will produce H20 and a rhodium(III) carbonyl.
This oxidized metal complex will be much poorer at
back-bonding into the CO than was the rhodium(I) in B, and
therefore its stretching frequency would be shifted nearer to
that for free CO (at 2143 cm 1). Finally, in Figure 7 are
presented data which illustrate the effect of increasing the
rhodium concentration on the rate of decomposition of the
intermediate. This rate was measured by monitoring the
electronic absorbance for C at 480 nm. It is evident that at
a threshold concentration in A between 0.98 x 10 ^ M and 1.47
x 10 3 M, the reaction of B to form C becomes autocatalytic
in character. At 0.98 x 10 3 and 0.68 x 10 3 M this reaction
follows a much more regular course. These results indicate
that a free radical decomposition of intermediate B is a
sustained process only above the threshold rhodium
concentration. Indeed, the electronic absorption spectra
indicate that at much high concentrations, reaction 7 is less
specific to the exclusive formation of C. In this case the
band at 480 nm for C is present only as a plateau due to the
absorbance of a secondary rhodium(III) product which absorbs
at lower wavelengths.
The characterization of intermediate B and the rate law
in eq. 10 have an importance not yet discussed. They
indicate that in reaction 7, hydroperoxide is initially
formed from the Bronsted acid catalyzed reduction by dioxygen
by ethanol or isopropyl alcohol solvents (eq. 15). The

Figure 7.
Demonstration
of RhCl
of
>CH
,(H20) 2 « 2
concentration (profile
in
(B)
Rh(CO)pC1
0.98 xKT
the autocatalytic formation
-jCH^OH above the threshold
A). Concentrations
are for (A) 1.47 x 10,"' M;
M; and (C) 0.68 x 10 j M.

Absorbonce

35
CH3CHROH + 02 -»• CH3CRO + HOOH (15)
R = CH3 or H
oxidation of primary and secondary alcohols to aldehydes and
ketones using dioxygen has been known for some time.'*5'^
These oxidations may be divided into two categories: (1)
free radical initiated reactions, using asoisobutyronitrile
(AIBN) for example, and (2) metal-catalyzed oxidations. The
principal difference is that oxidations of the first type may
9
produce HOOH stoichiometrically (eq. 15) as long as
precautions are taken to stabilize hydrogen peroxide while
oxidations of the second type produce water^ (eq. 8),
because the metals which catalyze HOOH formation also
catalyze decomposition of hydroperoxides to H20 and 0^ very
efficiently. Thus, there is literature precedence supporting
our proposal that HOOH is produced (albeit inefficiently)
37
with a Bronsted acid as a catalyst.
Under our reaction conditions the HOOH concentration
reaches a very low steady-state value, accounting for the
slow initial rate of oxidation of A (eq. 7) and our inability
to detect HOOH by iodometric techniques in acidic ethanol
solutions under 0^. However, we have obtained indirect
evidence of HOOH production in two series of experiments in
which H+, Cu(II) and Rh(III) were checked for their ability
to (1) speed up the oxidation of A (eq. 7) by producing HOOH

36
catalytically from the alcohol reduction of C>2 and (2)
catalyze the oxidation of isopropyl alcohol (eq. 8) as
measured by acetone production. For the investigation of the
effect of these three reagents on the rate of oxidation of A
(eq. 7), we worked at 1 atm rather than at 80 psi of 02
(5.4 atm) because the reaction is much slower at this reduced
pressure. As shown in experiment D in Table I, no final
product is observed at 480 nm in the electronic absorption
spectra in the absence of HC104, Cu(II) or Rh(III) after 1
hour, and the reaction take 36 hours to come to completion.
In contrast, the addition of 0.1 equiv of Cu(II) or Rh(III)
at the beginning of the oxidation of A (eq. 7) results in a
much faster reaction, with Cu(II) being most efficient
(experiments A and B). Doubling the acid concentration also
speeds up the reaction but to a much lesser extent
(experiment C). From these data it appears Cu(II) and
Rh(III), and to a much lesser extent H+, catalyze the
production of HOOH from ethanol reduction of 0^, and this
causes the increased rates observed for the oxidation of A
(eq. 7) in their presence.
Substantiation of this was found from our investigation
of the effectiveness of Cu(II), Ru(III) and H+ in catalyzing
the oxidation of isopropyl alcohol (eq. 8). Their
effectiveness at the beginning of this reaction follows the
order Cu(II) 'v Rh(III) >>H+, with rhodium resulting in 19
turnovers (acetone/rhodium) in 25 h and H+ producing only a
3 8
trace amount of acetone. The consumption of dioxygen when

37
Rh(III) was used for reaction 8 was also followed on a gas
burette for several hours and is linear over that time,
indicating this catalyst is not slowly .rendered inactive. It
is reasonable to suggest that HOOH, or peroxo metal
complexes, are formed as intermediates in reaction 8 and that
the efficient catalysis of this oxidation is evidence of
the ability of a reagent to catalyze the production of
peroxide from the alcohol reduction of 02. Because both
Cu(II) and Rh(III) are efficient hydroperoxide decomposition
catalysts, the HOOH is produced at a very low steady-state
concentration and may in fact never leave the coordination
sphere of the catalysts.
Experiment E in Table I demonstrates unequivocably that
an intermediate oxidant (HOOH) is formed in the presence of
only HCl, HC104, ethanol, and 0^. This has been labled an
"incubation" experiment because it involved stirring 3.2 x
10 ^ M each of HCl and HC10. in ethanol under 1 atm of 0_ at
4 2
40°C for 48 hours, followed by the addition of the [Rh(CO)2~
C1 ]2 to initiate reaction 7. In this case upon adding A no
induction period was observed and the reaction was complete
in only 7 hours compared to the 36 hours necessary when
mixing all reagents from the start. In agreement with the
rate law in eq. 10, this further indicates that the first
step in the oxidation of A involves the production of HOOH
from H+, 02 and CH^CH^H and that hydroperoxide is the
reagent directly responsible for the oxidation of [Rh(CO)2~

38
Table I. Oxidation of [Rh(CO)2C1]2.
Experiment
Catalyst3 at
Relative
Absorbance
for Complex C
480 nm at 1.0 h
Time for
Completion of
Reaction 7
A
0.15 mM Cu(II)
14
4
B
0.17 mM Rh(III)
3
10
C
4.2 mM HC104
ob
14
D
None
0
36
E
"Incubation"0
1
7
aThese reactions were run at 40°C and 1 atm of 02, using
0.80 x 10-3 M [Rh(CO)2C1]2, 3.2 x 10*3 M HC1, and 22.5 mL of
ethanol as solvent, in addition to the catalyst listed.
bNo final product II could be detected after 1.0 h.
c . “3
This run involved stirring 3.2 x 10 M HC1 and
3.2 x 10 3 M HCIO^ in ethanol at 40°C and 1 atm of 02 for
48 h, followed by the addition of [Rh(CO)9C1]2 to a
0.90 x 10
M concentration.

39
Cl]2 to rhodium(III) chloride in ethanol via a hydroperoxo-
rhodium complex intermediate. Our proposed mechanism for
this oxidation is shown in Scheme I and is substantiated by
all of the preceding evidence and arguments.
Scheme I
CH3CHROH + 02 CH3CRO + HOOH (a)
[Rh ( CO) 2C1 ] 2 + 2HC1 + 2H00H
2 [Rh(CO)Cl2(00H) ]2_ + 4H+ + 2C0 (b)
[Rh(CO)Cl2(00H)]2_ + 2H+ ^ [Rh(CO)Cl2(00)]3~ + 3H+ (c)
[Rh(C0)Cl2(00) ]3_ + 4H+ + Cl" + CH3CHR0H -*â– 
RhCl3(H20)2•CH 3CHR0H (d)
An intermediate analogous to B is not produced when
[Rh(CgH^4)2C1]2 is used instead of [Rh(CO)2Cl]2 as the
rhodium(I) starting material in a reaction similar to that in
eq. 7. In this case the reaction to form rhodium(III)
chloride is complete in only 40 min (compared to 12 hours
under identical conditions with A), and no evidence for
intermediates is found in the electronic absorption spectra.
In contrast, [Rh(P(tolyl)3)(CO)Cl]2 is not oxidized to
rhodium(III) chloride even after 48 hours.

40
Since Scheme I requires solvent reducing equivalents to
produce HOOH and subsequently [Rh(CO)CI2(OOH)] from 0^, any
solvent capable of this 02 reaction could lead to the
oxidation of A by this mechanism. Indeed, we have found that
methanol, ethanol, isopropyl alcohol, and to a lesser extent
tetrahydrofuran (THF), all produce B as an intermediate in
the oxidation of A by 0^. In THF this could appear through
the intermediacy of THF hydroperoxide, produced from the
abstraction of an a-hydrogen atom by and a subsequent
radical coupling reaction. The THF-hydroperoxide may react
with [Rh(CO)2CI]2 as both HOOH and t-BuOOH. In contrast,
use of the typically nonreducing solvents tert-butyl alcohol,
39
acetone, and N,N-dimethylformamide (DMF) does result in
oxidation of [RhtCO^Cl^ without forming B as a stable
intermediate. In tert-butyl alcohol and acetone the reaction
is very fast, finishing in 40 min under conditions for which
it takes 10 hours for completion in ethanol. In DMF the
reaction is much slower (also taking 10 hours) and was
monitored by electronic absorption spectroscopy. In this
solvent only one isosbestic point is observed (at 390 nm) due
to the production of rhodium(III) trichloride from the
oxidation of [RhiCO^Cl^ without the formation of any stable
intermediates (Figure 8).
It is interesting that the oxidation of A (eq. 7)
proceeds through the coordination of HOOH to [RhtCO^Cl^ in
primary and secondary alcohol solvents rather than proceeding

Figure 8. Series of visible spectra for the 0^
oxidation of [RhiCOi^Cl]^ to rhodium(III)
trichloride in DMF as solvent.


43
by the alternative mechanism that seems to occur in tert-
butyl alcohol, acetone and DMF. When THF is used as solvent
the reaction is much faster and only poor resolution of the
electronic absorption band due to B is observed. This is due
to a lower concentration of B relative to that found in the
alcohols, and possibly a low energy absorption band.40 In
THF it may be that both mechanisms are functioning, which
would explain the low concentration of B observed. It is
important to note that we cannot rule out the alternate
mechanism occurring in methanol, ethanol, and isopropyl
alcohol solvents to a small degree. However, it is evident
from the magnitude of the bands due to B in the electronic
absorption and infrared spectra, as well as data from the
kinetic rate law in eq. 10, that Scheme I involving the
coordination of HOOH to [RhiCO^Cl^ is dominant in primary
and secondary alcohols.
Conclusion
It is usually necessary to include bio-type or
Schiff-base ligands in order to prepare a hydroperoxide
complex, which makes the characterization of B as [Rh-
(CO)Cl^(OOH)] noteworthy. The CO ligand seems to be
responsible for at least some amount of the stability of this
complex. It is this stability which does not lead to the
characterization of the complex as an intermediate in the
catalytic oxidation of 1-hexene to 2-hexanone. Complex B

44
appears to have only slight (if any) reactivity as a catalyst
for 1-hexene oxidation. This result is not unexpected when a
comparison is made between the rhodium(III) active catalyst
and the rhodium(I) hydroperoxo complex, B.
The fact that primary and secondary alcohols can form
low concentrations of HOOH from the reduction of 02 may also
have several implications. Other metal complexes may have to
be included with H+, Cu(II) and Rh(III) as catalysts for the
alcohol reduction of 02 to HOOH. Systems which require long
term exposure to alcohol and 02 may find the low
concentrations of HOOH produced to be quite significant.
Substrate oxidations of 0^ via HOOH formation may also be
more prevalent than now realized.
Further results have shown HOOH and t-BuOOH to both be
effective reagents in the RhCl^'3H20 catalyzed oxidation of
1-hexene to exclusively 2-hexanone in the absence of 0^. The
results are the same whether the solvent is ethanol or tert-
butyl alcohol (which has no reducing equivalents). These
facts provide still further justification for the character¬
ization of the active catalyst for reaction 1 as a
rhodium(III) chloride complex.
Experimental Section
All solvents and reagents were of reagent grade and
used without further purification. Literature methods were
used to prepare [Rh(CO)2C1]2.41 Hydrogen peroxide and tert-
41

45
butyl peroxide were used as 30% and 70% aqueous solutions,
respectively, and were standardized iodometrically. The
acids HC1, H2S04, and HC104 were used as their concentrated
aqueous solutions.
Infrared spectra were recorded on a Nicolet 7000 Series
Fourier transform infrared spectrometer. GLC spectra were
obtained with a Varian Model 940 FID instrument using a
3-m,l/16 in. i.d. copper column packed with Chromasorb P
supported diethylene glycol adipate. For the detection of
acetone a column temperature of 60°C was employed, and the
measurement of 2-hexanone was quantitated by using
2-heptanone as an internal standard. The electronic
absorption spectra were recorded on a Cary 14, and all
samples were run in air at ambient temperature and pressures.
Care was taken to verify that the intermediates monitored by
this technique were stable over the course of the measure¬
ments. The molecular weight of C was determined in methanol
by vapor pressure osmometry.
Catalytic Oxidations of 1-Hexene
All catalytic 1-hexene oxidations were run in 250-mL
Parr pressure bottles equipped with bras Swagelok pressure
heads. These were constructed to allow purging with C>2, as
well as sampling of the solution under reaction conditions
during the course of the reactions. 2-Hexanone production
was measured by GLC.
A typical catalytic reaction was run as follows: to a
250-mL Parr bottle were added 0.074 mmol of [Rh(CO)' ]BF.
L 2 n 4

46
2
(prepared as earlier reported and used immediately),
0.0171.g of Cu(N03)2•2.5H2 (0.074 mmol), 0.0219 g of NaCl
(0.375 mmol for the case in which 5:1 mole ratio chloride/
rhodium was desired), 0.41 mL of 0.36 M H2SC>4 (0.148 mmol as
an ethanol solution prepared from aqueous concentrated
H2S04), 0.568 mmol of 2-heptanone, 45 mL of absolute ethanol,
and 15 mL of 1-hexene (purged through alumina to remove
peroxides). This mixture was purged 5 times with 60 psi of
02, set to 40 psi of C>2, and the reaction initiated by
placing in a 70°C oil bath.
Preparation of RhCl^(H20)2CH3CH2OH (II)
Compound C was prepared for characterization studies
most easily under 40 psi of 02 at 70°C by mixing 0.0514 g of
[Rh(CO)2Cl]2 (0.132 mmol), 1.10 mL of 0.48 M HCl (in ethanol,
0.528 mmol), and 15 mL of ethanol. This produced a bright
orange solution after a reaction overnight, from which C was
isolated by rotovapping to dryness and drying in vacuo. The
for H402Cl3Rh caled. 245; found, 226. Anal. Caled for
C2H10°3C13Rh: C' 8*24; H' 3.46; Cl, 36.50. Found: C, 8.41;
H, 2.69; Cl, 37.17.
Determination of Acetone Production
In Presence of 1-Hexene. The measurement of acetone
produced in the initial stage of the Rh/Cu-catalyzed
oxidation of 1-hexene with isopropyl alcohol as solvent was
made by GLC as follows: To a 50-mL round-bottom flask were

added to 0.159 g of RhCl^'Sf^O ( 0.605 mmol), 0.137 g of
Cu(NO^)2'2.5H20 (0.589 mmol), and stir bar. This was purged
20 min with 02 at 40°C and 30 mL of an C^-purged, 9/1 (v/v)
solution of isopropyl alcohol/l-hexene added to initiate the
reaction. GLC's were recorded after 4, 8, 17, 25 and 40 min.
The amount of acetone produced was determined by comparison
of peak heights with standards at the same time under
identical conditions. When this 1:1 Cu/Rh ratio was used,
0.5 mol of acetone was formed per mole or rhodium in the
first 4-8 min. No further production was observed. When a
2:1 Cu/Rh mole ratio was used, continuous, catalytic
production of acetone was observed.
In Absence of 1-Hexene. The catalytic production of
acetone from the 02 oxidation of isopropyl alcohol was
observed when 1-hexene was excluded from the solutions. Both
RhCl^-3H20 (0.140 mmol) and a stir bar were placed in a 15-mL
round-bottom flask and purged 20 min with 02 at 40°C. Into this
was syringed 7 mL of isopropyl alcohol, purged itself with
02 at 40°C, to initiate the reaction. Acetone production was
measured as described above.
Titration of [RhtCO^ClK with HOOH
Because the reaction of HOOH with Rh(CO)2Cl2 (A) is
quite slow in ethanol, it was run at 40°C. The visible
spectrum of the intermediate, [Rh(CO)Cl2(00H)] (B), is not
clearly observed by first adding 1.0 equiv of HOOH, followed
an hour later by 0.5 equiv. The first addition causes the

48
reaction of much of the starting material A (which overlaps
the band at 385 nm), so that after the second addition the
band due to C at 385 nm is easily observable in the
electronic absorption spectrum. Intermediate B is easily
detected in the oxidation of A by HOOH by using FT-IR. Since
there is no overlap of the carbonyl bands of A and B, the
intermediate is detected in the first addition of HOOH.
Immediately after use HOOH was diluted in ethanol. Aqueous
dilution causes the addition of too much H20, which retards
the reaction considerably.

CHAPTER III
ENHANCED SITE ISOLATION ON SILICA GEL
AND IMPROVED LIFETIMES OF SITE ISOLATED CATALYSTS
Introduction
Functionalized polymers have been increasingly employed
to support transition metal complexes as catalysts in recent
years. There have been several reviews in the literature
involving both organic supports4^ 4^ and inorganic
solids.4® 50 The system of interest here involves
functionalized supports which usually contain molecularly
definable species. Such systems are largely in the minority,
because they do not include either (1) the deposition of
metals or metal oxides by the oxidation or reduction of metal
complexes, or (2) the intercalation of metals in
unfunctionalized inorganic oxides.
The lack of physical methods which can routinely
provide identification of surface supported metal complexes
hinders the development of new catalytic systems. As a
result, attempts to prepare supported catalysts are often
based upon known homogeneous systems. The approaches for
49

50
attaching metal complexes is often guided by the ligand
system of the homogeneous catalyst. The methods which have
been utilized include ligand exchange or substitution of the
51 5 2
metal complex to the support, ' addition to unsaturated
metal complexes,^^^ and ionic attachment. ^ ^
Immobilization of metal complexes on solid supports can
provide advantages over both homogeneous and heterogeneous
catalysts. Included in these are (1) the ease of separating
solid catalyst from the reaction mixture, which encourages
the use of flow reactors, (2) the ability to greatly increase
dispersion of the metal on the surface, allowing the use of
less metal (and finances), and (3) reduced contact with the
reaction vessel leading to reduced corrosion. This potential
for gaining the advantages of both homogeneous and
heterogeneous catalysts has many industrial applications
which are being investigated.
Following below is a brief discussion of the general
properties of the inorganic solid, silica gel, which is used
as a catalytic support in the research presented in this
chapter.
Silica gel has a surface which is very irregular
consisting of hydroxyl and silicon bridging oxide groups. It
is quite rigid and contains many channels throughout its
structure and only the silica gel surface may be functional¬
ized. Silica gel samples which vary widely in surface area
are available. Several characteristics of silica gel make it
potentially preferable to organic polymers as a support for

51
metal complexes. The rigidity of its silicon oxide tetra-
hedra is often an advantage for immobilizing and site
isolating catalytic centers. The stability of silica gel at
higher temperatures than organic polymers may also be
important. Finally, the large number of organosilanes which
are becoming commercially available and the mild conditions
under which functionalization is achieved makes the number
of possible silica supported moieties quite large.
As mentioned above, organosilanes are employed to
functionalize the surface of silica gel. It has been
reported that the reaction proceeds by hydrolysis, hydrogen
bonding and final bond formation as shown in Figure 9 as
reactions a-c.57 The symbol [SG]-OH is used to represent
unfunctionalied silica gel.
An investigation of the nature of the binding of
5 8
organosilanes to the silica surface was recently reported.
Before this study was reported, it was generally believed
that three bonds from the silane to the silica suface were
formed. However, in this report Waddell et al. state that most
commonly only one bond is formed from silane to silica, while
the formation of two bonds is possible, and tridentate
bonding seems unlikely due to steric limitations.
Another important characteristic of polymer bound
metals is the ability to achieve site isolation of the metal
complex on the polymer surface. Solid supports can function
to avoid molecular aggregation and prevent the formation of
multinuclear complexes or clusters. This usually requires

Figure 9. General reaction scheme for the functional¬
ization of the surface of silica gel,
[SG ]-0H.

53
R3SiCl + H20
R3Si(OH) + HC1
(a)
R3Sí(OH) + [SG]-OH
[SG ]-0 H OH ( S i ) R 3
(b)
[SG ]-0--H OH(Si)R3
[SG ]-0(SÍ)R3 + H20
(c)

54
dilution of active sites on the surface in order to minimize
contact of supported metal complexes, although another method
has been successful at achieving site isolation (vide infra).
Most of the work reported in supporting metal catalysts has
employed very large loadings of the polymeric surface with
the desired functional group and metal complex. In these
cases elemental analyses can often be utilized, which is
advantageous since there are so few physical methods avail¬
able. However, this has led to a lack of research on systems
with definite site isolation of active species, or possible
improvement of existing catalysts by the establishment of
site isolation. Rigid, non-flexible polymeric supports such
as silica gel are usually required when attempts to obtain
site isolation of a supported species are undertaken.
There are several reports of functionalized silica gel
being used to achieve site isolation, and perhaps other
examples from industrial laboratories which have not reached
any available literature. Among the reported examples are a
bound imidazole iron tetraphenylporphyrin which is used to
59
reversibly bind dioxygen, and cyclopentadiene groups
supported on silica gel which form stable mononuclear iron
and cobalt carbonyl complexes.^

55
Results and Discussion
Polymer Support of the Catalyst
The oxidation of terminal olefins to 2-ketones
catalyzed by rhodium and copper was discussed in some detail
in the previous chapter in relation to its homogeneous
mechanisms. Here will be described an investigation to
increase that catalyst's relatively short lifetime by
attempting to provide an ideal supported environment for the
catalytic species. Prevention of the suspected deactivating
oxidative aggregation of the rhodium catalyst was the
rationale for this approach.
Required of a solid support is a solvent independent
rigidity which could improve prospects for obtaining site
isolation. Silica gel, unlike organic polymers such as poly¬
styrene, meets these requirements. Initial attempts at using
an organosulfide ligand on silica gel to bind the
rhodium/copper cocatalysts were successful.^ Goals of
improving the activity and lifetimes of supported catalysts
while gaining a detailed knowledge of the silica surface
precipitated the research described in this chapter.
Silica gel supported organosulfide samples (abbreviated
[SG]-SH) were synthesized using (3-mercaptopropy1)trimethoxy-
silane [ (CH^O) ^Si ( CH2CH2CH2SH )] reacted with plain silica
gel. A simple model was used to help gain insight into the
surface coverage on the silica gel. Approximating the

56
silicon-oxygen bond distance as two Angstroms and assuming
tetrahedral coordination around silicon, then the distance
O
between oxygen atoms of the surface silanol groups is 6.5 A.
In order to obtain an upper limit it is assumed that a flat
surface exists and that all of the surface groups are
silanols (-SiOH). Since the Davison Grade 62 silica gel
2
employed has a surface area of 340 m /g [SG], then there is
-9
approximately one surface hydroxyl group per 4.3 x 10 m of
surface. Thus, it can be calculated that as an upper limit
there are about one mmol of surface silanol groups per gram
[SG]. With this value it can be calculated that the [SG]-SH
samples prepared contain approximately 1/40, 1/20, 1/10 and
1/5 mmol sulfide/mmol surface Si (S/Si) which correspond to
0.025, 0.5, 0.10 and 0.20 mmol S/g[SG], The number of mmol
S/glSG] was determined by electronic absorption for all
samples as described in the experimental section and is
independent of the model and calculations discussed above.
The values for the number of mmol S/g[SG] varied only a small
amount between preparations of functionalized silica gels.
It was these experimental values which were employed to
determine the amount of silica gel necessary for each
catalytic oxidation. The general labels used to represent
[SG]—SH samples of different sulfide loadings are shown in
Table II.
Also worthy of consideration is the relatively large
potential surface area over which the supported rhodium
complex may cover due to its attachment to a chain of six

57
Table II. Representations used to designate [SG]-SH samples
of varying sulfide concentrations.
SH Loadings on [ SG ] Surface
0.025 mmole S/g [SG]
0.05 mmole S/g [SG]
0.10 mmole S/g [SG]
0.20 mmole S/g [SG]
1 surface -SH/ 40 surface
-SiOH
- 1S/20SÍ
- 1S/10SÍ
- IS/ 5Si

58
atoms. Despite not being linear, this chain still allows a
380 square Angstrom area over which each rhodium may migrate.
This number, along with the surface Si concentration, allows
the calculation that the silica surface must have a
concentration less than 1 S/g surface Si in order for site
isolation of the rhodium to exist. This is a convenient
number to which properties of actual [SG]-SH samples may be
compared.
Preparation of supported rhodium complexes on silica
gel was achieved by utilizing freshly generated [Rh(CO)' ]-
6 2
BF4 (S' = solvent) in ethanol or tetrahydrofuran (THF) as
shown in reaction 16.
[Rh(CO)2C1 + 2AgBF4 - 2[Rh(CO)2S' ]BF4 + 2AgCl (16)
This rhodium cation readily binds to lSG]-SH samples at room
temperature producing silica gels varying from bright yellow
to red-orange as the concentration of surface sulfide is
increased.
The carbonyl ligands in the rhodium complex bound to
the silica gel allows the use of infrared spectroscopy to
investigate the functionalized surface. In these studies
freshly prepared [Rh(CO)' ]BF4 (S' = solvent) was reacted
with [SG]-SH sample under nitrogen and an infrared spectrum
quickly taken. The supported rhodium complex produced on
many dilute functionalized gels (e.g., 1S/40SÍ) yields a
two-band infrared spectrum (2055 and 2005 cm ^) characteristic

59
of [SG]SRh(CO)2S1 (S' = solvent). More concentrated
[SG]-SH samples (e.g., 1S/5SÍ) treated identically produce
three-band spectra ( 2075(m), 2055(s), and 2005(s) cm-''’)
5 2
indicative of a supported dimer, ( [SG ]-S)2Rh2(CO) . These
different surface species are represented in Figure 10. It
seems very evident that concentration of surface sulfide
groups past a certain point removes site isolation and
permits supported rhodium dimerization. These trends and
their implications will be discussed further in later
sections.
Catalytic Oxidations of 1-Hexene by Supported Complexes
Silica gel organosulfide supports ([SG]-SH) as
described previously were used to immobilize rhodium and
copper in order to investigate in detail the heterogeneous
catalytic oxidation of 1-hexene to 2-hexanone (reaction 17).
I!
2CH2=CH(CH2)3CH3 + 02 - 2CH3C(CH2)3CH3
(17)
Electronic absorption (as described in the Experimental
Section) was used to quantify the amount of sulfide in each
silica gel sample. The amount of sulfide present determined
the quantity of [SG ]-SH used as a support in each catalytic
oxidation. Each oxidation to be discussed employs 0.074 mmol
of both [Rh(CO)_S' jBF. (S' = solvent) and Cu(NO-)_’ 3H_0.
2 n 4 3 2 2
The quantity of [SG]-SH which provides 0.16 mmol of sulfide

Figure 10.
Representation of the different supported
rhodium complexes obtained with (1) 1S/5SÍ-
[SG ]-SH and (2) site-isolated 1S/20SÍ-
[ SG ]-SH.

S¡\/\/SH
1) .20mmole S/g(SG)
S.^AsH RhC^BF4
SÍVVSH RT
ElOH
S¡^\X\sh
2) .OSOmmole S/g(SG
^—Y—sh
same
/n/^SH
(CC^Rh^ ^RhtX>2
-Sín^~'^
-Si
A
CO)2Rh RhCC^
Si NS/
—SRhC02Sn
sjW-SRh(CO)2S'n

62
sites (a 10% excess) is used in each oxidation. Also added
to each reaction were 2 equivalents of HC104 (based on moles
of rhodium), 15 equivalents of 2-haptanone internal standard,
45 mL absolute ethanol solvent and 15 mL 1-hexene substrate.
An apparatus of 250 mL Parr pressure bottles was used to
conduct the experiments along with a pressure head which
allowed the removing of aliquots of the reaction mixture
under reaction conditions. Reactions were initiated by
purging the pressure bottle containing all components of the
reaction five times with 60 psi 0^, setting the pressure to
40 psi C>2 and placing the apparatus in a 70°C oil bath. The
HC10. was used because Mimoun found a Bronsted acid to be
4
necessary when using rhodium(I) in his homogeneous
investigation, and it is given a role in his proposed
mechanism. Gas-liquid chromatography (GLC) was employed to
follow the catalytic oxidations. A calibration curve of
2-hexanone product versus 2-heptanone standard was used to
calculate 2-hexanone production in millimoles.
In preparing [SG]-SH supports, if it is assumed that
all of the added (CH^O)3SiCH2CH2CH2SH reacts completely, one
obtained values for [SG]-SH of 0.025, 0.050, 0.100 mmol
S/g[SG] corresponding to 1S/40SÍ, IS/ 20Si, and 1S/10SÍ,
respectively. The analysis for sulfide (using a rhodium
complex and electronic absorption as in the Experimental
Section) for a series of [SG]-SH samples produces values of
0.020, 0.041, and 0.076 mmol S/g[SG]. These values are
reasonably close to those expected for complete reaction and

63
also have relative ratios to one another very similar to
those which assume complete reaction. Again, it is the
experimental values for sulfide content which are used in
determining the quantity of [SG]-SH necessary for each
catalytic oxidation.
Results of the heterogeneous catalytic oxidation of
1-hexene to 2-hexanone are most clearly displayed as graphs
of mmol of product (2-hexanone) versus time (in hours).
Figure 11 shows the oxidation results characteristic of three
[SG]-SH samples which vary in sulfide loading. The samples
are referred to by a ratio of sulfide to surface silicon
atoms in the silica gel. These values are obtained by
assuming complete reaction when functionalizing the gels.
However, the experimental sulfide concentration values were
always used when determining the mass of silica gel necessary
for reaction. Each curve in the oxidation graphs represents
many experiments repeated with the same supply of
functionalized silica gel. Also, other samples were prepared
and compared to previous gels. The experimental sulfide
concentrations were very similar between silica gel batches.
The idealized S/Si ratios are then used for convenience in
referring to several different supplies of similar silica
gels.
In Figure 11, if all of the rhodium and copper is
effectively site isolated on these samples, then very similar
activity should result from each of the catalysts. The
1S/40SÍ (0.025 mmol S/g[SG]) sample, curve A, is less active

Figure 11.
Profiles for the oxidation of 1-hexene obtained at
70°C using lSG]-SH supported rhodium catalysts with
various loadings of organosulfide. (A) 1 surface
sulfide/40 surface silanol groups, 1S/40SÍ;
(B) 1S/20SÍ; (C) 1S/10SÍ.

time, hr
mmol 2-hexonone
S 9

66
for 2-hexanone production than the 1S/20SÍ and 1S/10SÍ
samples (0.05 and 0.10 mmol S/g[SG]). This results from
diffusion problems which will be discussed further later in
this chapter. Curves B and C do show similar activity for 24
hours as shown. Catalytic activity resulting from immobili¬
zation of the rhodium and copper complexes on silica gel
certainly has been demonstrated, and several comparisons to
these results will be made in following sections.
After establishing supported activity, it is important
to check for leaching of the metal complexes from the solid
into solution. Catalytic oxidations were run for three hours
and the solutions removed by syringe under reaction
conditions. The filtrate, after measuring the volume, was
then placed in a new Parr bottle with another equivalent of
Cu(II) and the oxidation re-started in the original manner.
The filtrate had activity ranging from 5 to 15 percent of the
total normal supported activity depending on the silica gel
sample being studied. Since the homogeneous rhodium/copper
oxidation catalyst is much more active than the corresponding
supported system, then it is apparent that the vast majority
of the heterogeneous catalytic activity is due to [SG]-SH
bound catalyst.
It is relevant to stress that experiments to check for
leaching must be done under reaction conditions. The
chemical equilibria involved in leaching may be greatly
affected by conditions milder than those during reaction and

67
thus leaching should be investigated only under reaction
conditions.
Alkyl Covering of the Silica Surface to Improve Site
Isolation and Catalysis
The silica gel supported catalytic system as described
until this point offers several characteristics which make it
ideally suited for further investigation of site separation
in a quantitative manner. Already demonstrated has been a
method for determining the surface loading of organosulfide
functional groups, a spectroscopic technique for establishing
the identity of silica gel immobilized rhodium species, and
an oxidation reaction which can accurately measure catalytic
activities and catalyst lifetimes. Thus, any further
attempts to alter the silica surface may be monitored rather
precisely.
The general supposition that increased site isolation
of the silica gel supported rhodium species is directly
related to increased catalytic activity is supported by the
results obtained using [SG]-SH as the support. Very highly
loaded [SG]-SH samples produce catalytic systems of very low
activity. Further manipulation of the silica gel supports in
order to produce better and/or longer lived site isolation
was greatly desired. It was assumed that the general
deactivation of the supported catalysts was dependent to some
degree upon the aggregation, over time, of rhodium species on
the silica surface. A mechanism could be logically
postulated whereby sulfide bound rhodium species exchange

68
with surface silanol protons and thus migrate along the
surface until aggregation occurs. As a result, a
modification of the silica surface was sought which could
remove this possible path of aggregation. One other goal was
to obtain a method for increasing the loadings of site
isolated species per gram of silica support.
The functionalization of unused surface silanol (-SiOH)
groups with alkylsilane moieties results in an effective
method for achieving the previously stated goals. Chloro-
alJcylsilanes are utilized to produce alkyl groups bound to
the silica surface. The reaction of the alkylchlorosilanes
with the silica surface is identical to the surface reaction
with (3-mercaptopropyl)trimethoxysilane as described in
reactions 1-3. The chloro group here reacts as does the
methoxy group in those reactions, forming HC1 instead of
CH^OH. Chlorotrimethylsilane, chlorotriethylsilane and
chlorotripropylsilane were each used to prepare silica gel
samples, along with the same (3-mercaptopropyl)trimethoxy¬
silane in each case. Samples prepared with alkyl groups and
the sulfide functionality on the silica surface will be
generally referred to as alkylated [SG]-SH, while those with
only sulfide will be called either non-alkylated [SG]-SH or
merely [SG]-SH. The functionalized silica gels will also be
identified by a ratio of surface sulfur to surface silicon
(S/Si) as described previously (e.g., 1S/10SÍ, 1S/20SÍ). The
alkylated gels will also be referred to by a percent
alkylation which is the percent of all unused surface silicon

69
atoms reacted with chloroalkylsilane assuming complete
reactions. The assumption of complete reaction is generally
supported by elemental analyses for carbon which became
possible at levels of substantial alkylation.
Quantitative analyses for sulfide were also done for
alkylated [SG]-SH samples. The values of mmol S/g [SG] for
these were generally slightly lower than for their
non-alkylated analogs. Again, the values obtained for
sulfide content were used to determine the necessary quantity
of silica gel for catalytic oxidations.
Infrared spectroscopy provided a good deal of
information concerning the properties of the alkylated [SG]
-SH gels. As described earlier, reaction of Rh(CO)_S' BF.
(S' = solvent) with [SG]-SH samples provides species whose
infrared spectra are quite useful. Rhodium species bound to
1S/40SÍ and 1S/20SÍ [SG]-SH gels produce the two band
infrared spectrum indicative of the monomeric supported
complex using both non-alkylated and alkylated [SG]-SH
samples. The IR spectrum which results using 1S/10SÍ
non-alkylated [SG]-SH indicates the presence of primarily
dimeric rhodium complex on the silica surface. This
generally supports the estimation discussed earlier in this
chapter that the silica surface must be on the average about
1S/9SÍ or more dilute in order to produce a system in which
most of the rhodium is site isolated. The alkylated [SG]-SH
gels (e.g., 80% methylated) produce the monomeric rhodium
complex on the surface as indicated by their infrared

70
spectra. The alkyl surface covering allows the formation of
a different surface species than its non-alkylated analog at
identical loadings of metal per gram of silica gel. A
mixture of monomeric and dimeric rhodium complexes is present
on the surface of 80% methylated 1S/5SÍ [SG]-SH, while
primarily the dimer is produced on 80% methylated 1S/2.5SÍ
[SG]-SH. These infrared spectra are shown in Figure 12. It
may then be concluded that the alkyl covering cannot prevent
rhodium dimerization on the silica surface past a certain
level of metal loading on the silica gel.
Catalytic Oxidations Using Alkylated Silica Gels as Solid
Supports
The experimental procedures for conducting catalytic
oxidations using alkylated [SG]-SH supports are identical to
those for the non-alkylated systems described in Section B.2.
Again, the most effective way to present data for these
catalytic oxidations is in the form of graphs of millimoles
of 2-hexanone product versus time as measured in hours.
The oxidations obtained using [SG]-SH with 50% of its
available surface covered with trimethylsilyl group (50%
methylated) as supports for the rhodium and copper
cocatalysts are shown in Figure 13. Not only do these
catalysts demonstrate much greater initial activity in some
cases than their unmodified (non-alkylated) counterparts in
Figure 11, but they are still more active after 24 hours.
The 1S/20SÍ (0.05 mmole S/G[SG]) 50% methylated gel in curve

Figure 12.
Infrared spectra for immobilized [Rh(CO)_-
(C-Hj-OH) ] BF . using [SG]-SH supports witn
(AT IS/10SÍ 50% Me; (B) 1S/5SÍ 80% Me; and
(C) 1S/2.5SÍ 80% Me.

72
I I 1 I
2300 2000
(cm'1)
_l
1800
1

Figure 13. Oxidations using [SG]-SH supports which have some
portion of the silica surface covered with
trialkylsilyl groups. (A) 1S/40SÍ 50% Me;
(B) 1S/20SÍ 50% Me; (C) 1S/10SÍ 50% Me.


75
B produces virtually linear 2-hexanone production over 24
hours. Compared to the non-alkylated catalyst curve B of
Figure 11 on almost two-fold increase in product has been
obtained after 24 hours and a very active catalyst remains.
At the end of four hours essentially the same amount of
2-hexanone had been produced by curve B in Figures 11 and 13.
Infrared spectra indicated that in both catalysts the
essential species was monomeric rhodium complex before the
start of catalysis. Thus, alkylation of silica gel in this
instance has greatly enhanced catalyst lifetime.
Comparison of lS/lOSi catalyst systems from curve C of
Figures 11 and 13 reveals that the methylated catalyst is
superior almost from the very start of the oxidation. This
result correlates well with the fact that the non-alkylated
catalyst is composed of rhodium dimer, while the alkylated
one contains monomeric rhodium before reaction. This
demonstrates that higher loadings of catalytically active
complex can be obtained under site isolated conditions by
diluting the functionalized reagent in the hydrocarbon matrix
formed by -Si(CH^)^. A very active catalyst is still present
after 24 hours.
A surprising result is represented by curve A in
Figures 11 and 13. According to infrared spectroscopy site
isolation (rhodium monomer) exists in both systems before
reaction. The diffusion problem described in relation to
Figure 12 has apparently been decreased by the greater
affinity of alkene for the alkylated surface than for

76
solvent. Such a rationalization explains the greater initial
activity of curve A in Figure 13 versus Figure 11 as well as
the increased activity after 24 hours.
Figure 14 shows the results of 1-hexene using catalysts
supported on 50% and 80% ethylated silica gels. They are
generally more active than the non-alkylated gel catalysts
and are still very active after 24 hours. The 1S/10SÍ 80%
ethylated catalyst (curve E) is less active and the 1S/20SÍ
80% ethylated gel (curve D) more active than might have been
predicted. Samples which were 80% methylated yielded results
similar to those of the 50% methylated gels. It is also seen
in Figure 14 that increasing the percent alkylation does not
have a drastic effect on catalytic activity.
The 80% propylated [SG]-SH samples produce catalytic
results very much like those of the non-alkylated silica gels
of Figure 11. Figure 15 displays oxidations run for longer
time periods, each done with 1S/20SÍ [SGj-SH gels which have
different surface modifications. The 80% methylated gel
(curve B) is still active after 140 hours. It can be seen
that the 80% ethylated gel is less active than the methylated
one, while the propylated catalyst is nearly identical to the
non-alkylated sample. The propylated silica gels, and to a
lesser extent the ethylated ones, are markedly slow in
"wetting" by ethanol. Perhaps it is this increased
hydrocarbon-like nature of the surface which accounts for
their decreased efficiency as catalytic supports relative to
the methylated gels. Thus, even though enhanced solubility

Figure 14. Oxidations of 1-hexene using [S
supports. (A) 1S/40SÍ 50% Et;
(C) 1S/10SÍ 50% Et; (D) 1S/20SÍ
(E) 1S/10SÍ 80% Et.
]-SH samples as
B) 1S/20SÍ 50% Et;
80% Et;

mmol 2 - hexanone
3.2
2.8 -
2.4
2.0
1.2
0.8 -
04 -
A
B
c
D
E
ISAo Si 50% Et
1 S/20 Si 50%Et
,s/l0 Si 50%Et
ls/20 Si 80%Et
ls/iO Si 80%Et
time, hr
00
O CD

Figure 15. Oxidations of 1-hexene over longer time periods
(A) 1S/20SÍ not alkylated; (B) 1S/20SÍ 80% Me;
(C) IS/2OSi 80% Et; (D) 1S/20SÍ 80% Pr.

A
IS /20 Si
Not Alkylated
B
,s/20 Si
80 % Me
C
,s/20 Si
80% Et
D
ls/20 Si
80 % Pr

81
of the alkene in the surface layer may occur, exclusion of
the solvent would inhibit the reaction.
An investigation was undertaken to determine whether
under conditions in which the large amounts of silica gel
used in 1-hexene oxidations when the 1S/40SÍ (0.025 mmol S/g
[SG]) gels are employed as catalyst supports diffusion might
become rate-controlling. A typical 1-hexene oxidation
employing 1S/40SÍ non-alkylated [SGj-SH was run. A second
oxidation using one-half the amount of rhodium and copper,
and thus one-half of the silica gel support, was also run.
All other initial conditions and amounts of reactants were
identical. Assuming that diffusion is not rate-controlling
the rate of this oxidation should have been one-half of the
original rate since the oxidation is first order in rhodium
concentration.*^ Figure 16 clearly shows the reaction with
one-half of the silica gel supported catalyst to have a rate
greater than one-half of the normal oxidation. The dashed
line C is one-half of the curve A. Thus, there seems to be
some reaction inhibition due to the large amounts of silica
gel support used in the 1S/40SÍ oxidations (9-12 g), which is
near the limit of the mass of gel which may be stirred in
this experimental apparatus. This result may be ued to help
explain why in general several 1S/40SÍ (0.025 mmol S/g[SG])
supported catalysts are not as active as their 1S/20SÍ (0.05
mmol S/g [SG ]) counterparts (e.g.,
Figure 11).

Figure 16.
Oxidations of 1-hexene used to investigate
diffusion problems. (A) A "typical" 1-hexene
oxidation using 1S/40SÍ [SG]-SH; (B) oxidation
using one-half of the amounts of 1S/40SÍ [SG]-SH,
rhodium catalyst and copper(II) used in (A);
(C) a representation of one-half of curve A.

time, hr
mmol 2-hexanone
CD
£ 8
SG + Rh(CO,)*+ CuOIH Y40 Si)

84
Possible Effects of a Different Rhodium Catalyst
Characterization
The design and implementation of the supported
catalytic systems have been based on Mimoun's
characterization of the active catalyst as a rhodium(I)
complex. The possible characterization of the catalyst as a
rhodium(III) species as discussed in Chapter II may have
several implications. Chloride ion may also be quite
important since 3-5 equivalents of chloride ion promote
better homogeneous oxidations using [Rh(CO > 2^'n]BF^ (S' =
solvent) and given that the most stable homogeneous catalyst
. 6 4
species may be rhodium chloride complexes of same type.
Chloride ion cannot be added to the [SG]-SH systems without
extensive leaching occurring. The possible use of a
supported multi- dentate ligand for the immobilization of a
rhodium(III) catalyst should be considered for future use.
It would also be of interest to compare the effects of
alkylation of a multidentate ligand silica gel support to
those presented here for a monodentate ligand system.
Conclusions
The spectral properties and catalytic behavior of the
described systems demonstrate that isolating functionalized
lSG]-SH groups with [SG]-SiR^ (where R is alkyl) leads to
some very pronounced changes. The stability of the
methylated catalysts is greatly enhanced over that of the

85
non-alkylated systems. On non-alkylated [SG]-SH it is
possible that the derivatized silanol groups may exchange
with protons on nearby silanol groups and thus migrate along
the surface, aggregate and become inactive. The alkylated
gels remove -OH groups and would be able to effectively
suppress such a process leading to a longer lifetime for
site-isolated conditions. The mixing of reagents prior to
functionalization also ensures a better distribution of
functional groups over the surface under site isolated
conditions and enables one to attain a more concentrated site-
isolated catalyst.
In the specific catalytic system studied, increasing
the length of the alkyl chain covering the silica surface to
ethyl and propyl decreases catalytic activity over the methyl
covering. This may be due to solubility properties as
discussed earlier, or perhaps due to increased efficiency at
keeping the two cocatalysts apart. This approach should
still find general application and utility in the area of
hybrid catalysts where site isolation is a desired feature.

86
Experimental
General Procedures
All solvents and reagents were of reagent grade and
used without further purification unless otherwise specified.
The [Rh(CO)-Cl ]-41 and [Rh(CO)-,S' IbF,62 (S' = solvent) were
prepared as reported in the literature or purchased from
Aldrich and recrystallized from n-hexane. The (CH^Q) ^Si (Ci^Ct^-
CH^SH) and ClSiiCH^)^ were obtained from Aldrich and
CISi ( C2H,-) .j and ClSiiC^H.^)^ from Petrarch Systems. Silica
gel was grade 62 from Davison Chemical.
Infrared spectra were recorded on a Perkin-Elmer model
283B infrared spectrometer. The GLC were obtained with a Varían
model 940 FID instrument using a 3m, 1/16 in. i.d. copper
column packed with Chromasorb P supported diethylene
glycoladipate or with a Varian model 3700 FID chromatograph
using an 8 ft, 1/8 in. column of the same material. The
2-hexanone production was quantified using 2-heptanone as an
internal standard. Electronic absorption spectra were taken
on a Cary 14, and all samples were run in air at ambient
temperatures and pressures.
Preparation of Silica Gel Supports
All reactions of functionalizing silanes with silica
gel were done under argon with xylenes as solvent. Silica
gel was stirred in xylenes under argon, followed by heating,
and then a solution of one or more silanes in xylenes was

87
added dropwise to the hot silica gel slurry. The non-
alkylated [SG]-SH gel was made by adding (CH^O)3Si(CH2CH2~
CH2SH) to the gel. The [SG]-SH alkylated gels were made by
adding a solution of the mercaptosilane mixed with R^SiCl (R=
CH-j, C2H5 or ) . This technique is preferable to adding
each silane in separate steps. After refluxing 24 hours, the
silica gels were thoroughly washed with xylenes, ethanol and
then dried at ^90°C. The silica gels remain white in
appearance.
Determination of -SH on Silica Gel
Silica gel and its surface silanol groups were reacted
with (CH30)3Si(CH2CH2CH2SH) to produce the [SG]-OSi(OCH3)2~
(CH2CH2CH2-SH)(abbreviated as [SG]-SH). R3SiCl (R=methyl,
ethyl or propyl) was used to complete reaction of the silanol
groups and cover the silica gel surface with alkyl groups.
Evidence that trialkylsilyl groups are bound to the surface
is obtained by a substantial increase in the percent carbon
found in the elemental analyses and by an increase in the
lifetime of the functionalized catalyst.
Electronic absorption was used to determine the amount
of sulfide on each silica gel sample ( [SG]-SH). The [SG]-SH
samples were stirred with freshly prepared [Rh(CO)2S' ]BF4
(S' = solvent), the solid filtered off and the electronic
absorption spectrum of the filtrate taken. From a
calibration curve of the rhodium complex concentration versus
its absorbance at 390 nm the amount of rhodium in the
filtrate is measured. The amount of rhodium on the gel is

88
determined by the difference of the known initial amount of
rhodium and the amount of rhodium in the filtrate. Assuming
complete reaction of one rhodium per sulfide, the amount of
rhodium is equal to the amount of sulfide on the silica
surface. An analysis of this type was done for all samples.
Samples were prepared which varied in surface sulfide
concentration and in percent of available surface silanol
groups which were "alkylated" (reacted with trialkylchloro-
silane). Assuming tetrahedral coordination around silicon
and oxygen atoms with an approximate silicon-oxygen bond
distance of two Angstroms, and assuming that as an upper
limit a flat surface exists with all surface groups being
O
silanols, a separation of 6.5 A exists between the oxygens of
surface hydroxyl groups. This corresponds to one surface
-19 2
hydroxyl per 4.3 x 10 m of surface so it can be
calculated that as an upper limit there are about one mmol
surface silanol group atoms per gram [SG]. With this value
it can be determined that the [SG]-SH samples prepared
contain approximately 1/40, 1/20, 1/10 and 1/5 millimoles
sulfide/millimole surface Si (S/Si) which corresponds to
0.025, 0.05, 0.10, 0.20 and 0.40 mmol S/g[SG]. Silica gel
samples used as catalytic supports will be referred to by a
(S/Si) ratio and by a number of mmole S/g[SG]. In some
instances the percent alkylation (methylation, ethylation or
propylation) of the surface silicon sites will also be used.

89
Catalytic Oxidations of 1-Hexene
All catalytic 1-hexene oxidations were run in 250 mL
Parr pressure bottles equipped with brass Swagelok pressure
heads. These were constructed to allow purging with 0^, as
well as sampling of the solution under reaction conditions
during the course of the reactions. The 2-hexanone
production was measured by GLC.
All catalytic reactions were run using 0.074 mmol
[RhtCO^S'n]BF4 (prepared as reported earlier and used
immediately) and 0.0179 g Cu ( NO^ ) 2 • 3^0 (0.074 mmol). The
amount of silica gel employed was varied to provide enough
-SH sites to bind ail of the rhodium and copper with a 10%
excess (e.g., 4.9 g of 1S/20SÍ 80% Et [SG]-SH). Both metal
ions are attached to the [SG]-SH samples through the -SH
moiety producing a lemon-yellow to yellow-green supported
catalyst. The catalyst was added to a 250 mL Parr bottle
along with 0.32 mL 0.47 M HC104 (0.150 mmol, as an ethanol
solution prepared from aqueous cone. HCIO^), 1.136 mmol
2-heptanone, 45 mL absolute ethanol, and 15 mL 1-hexene
(purged through alumina to remove peroxides). This mixture
was purged 5 times with 60 psi C^, set to 40 psi 0^, and the
reaction initiated by placing the system in a 70°C oil bath.

CHAPTER IV
THE SYNTHESIS AND CATALYTIC APPLICATIONS
OF A MULTIDENTATE LIGAND AND CORRESPONDING METAL COMPLEXES
BOUND TO SILICA GEL
Introduction
The use of a polymer as a support for catalysts was
discussed in Chapter III for a specific system which employed
a monodentate chelate on silica gel. The general use of
polymers as supports for catalysts and chelates, and also as
synthetic reagents, has developed enormously since their use
in peptide synthesis was shown by Merrifield approximately
twenty years ago.^^ It was generally assumed for several
years that there was little, if any, interaction between
functionalized sites on resins such as polystyrene. This is
now known not to be the case, and Chapter III demonstrated
some of the rather stringent conditions which must be met in
order to achieve site isolation on a support such as silica
gel.
90

91
Another general approach to preparing stable polymer
bound metal complexes is that of first attaching a
multidentate ligand system to a polymer backbone and then
adding the metal ion to the previously formed ligand. There
have been many reports discussing polymers which contain
chelating groups of various sizes and donor atoms.An
excellent review of this area is cited here as reference 70.
Most of the polymer bound chelates studied are mono- or
bidentate, with only a few tri- and tetradentate systems
having been investigated.^^ Resins with bidentate
chelate groups often must provide a metal ion with two or
three chelating groups since many metal ions prefer forming
four or six coordinate complexes. This led to the common use
of uncrosslinked or lightly crosslinked polymers. The
ambiguity involved in trying to characterize these polymer
bound metal complexes makes it very difficult to interpret
data from catalytic reactions or physical methods.
In virtually all of the literature reports cited in
this area, there is no attempt made to isolate functionalized
sites from one another and in many cases two or more sites
must interact in order to provide successful chelation.
Chapter III discussed in detail the conditions required
to achieve site isolation on silica gel and surface
modifications which may enhance that isolation. The initial
sections of this chapter will discuss the preparation of a
stable multidentate ligand site isolated on silica gel which
can complex a variety of metal ions into polymer bound

92
complexes of a known geometry. Investigations of several
applications of these polymer bound complexes will then be
presented, followed by investigations into the use of
different solid matrices as chelate metal complex supports.
The ligand prepared on silica gel is a pentadentate
ligand which complexes several different metal ions. The
silica gel supported complex of iron(III) was used to
investigate some known homogeneous reactions.
Biological oxidation processes are generally quite
selective and sensitive and as a result attract the attention
7 2
of many chemists. Cytochrome P-450 is one enzymatic system
which can catalyze several types of oxidative
transformations, including selective alkane hydroxylations
and has therefore been an object of much research effort.
Several studies have proposed intermediate high-valent
oxometalloporphyrin species in the catalytic cycles of
7 3 7 4
several heme-containing oxygenase enzymes. ' Simple
chemical models for cytochrome P-450 were sought in order to
provide insight into some of the basic processes involved in
its chemical reactivity. A significant finding was the
realization that iron,75 chromium,76 and manganese77
porphyrins could catalyze oxygen transfer from iodosylbenzene
7 8
to simple hydrocarbons. In all of these cases, a metal-oxo
species is proposed as an intermediate, although complete
mechanistic details have not been determined. However, it
was the possibility of generating silica gel supported iron
or manganese oxo species to achieve some type of oxidative

93
transformation which was the impetus behind the work reported
here. The ability to form supported cobalt-dioxygen
complexes (vida infra) helped to encourage the idea that it
would be sterically possible to generate the supported iron
or manganese oxo intermediates. Another goal was to
determine the effect of limiting or eliminating interaction
between metal centers via their support and site isolation on
silica gel.
Another topic briefly investigated is the long known
"Fenton chemistry" of iron salts and hydrogen peroxide
7 9
affecting the hydroxylation of organic substrates. This
area has recently been reinvestigated by Cheves Walling and
ne gives an excellent overview of this area in reference 80.
The original goal of achieving this type of peroxide induced
oxidation with a supported iron complex was not realized due
to the leaching of metal complex into solution in the
presence of acid and peroxide. Thus, no mechanistic or
catalytic information is provided, although some further
knowledge of the silica surface is obtained.
Catalytic processes which require two different metals
have not achieved much success in being supported on
polymers. A method which may successfully attain support of
both metals is that of incorporating one active metal into
the structure of the support while supporting the other metal
on the surface of the solid. Incorporation of copper(II)
ions into silica gel is described along with attempts at
catalysis by resulting bimetallic systems.

94
The method of electron spectroscopy for chemical
analyses (ESCA) holds promise for studying the surfaces of
81 8 2
solid catalysts. ' The technique basically involves the
measuring of the energy spectrum of the electrons ejected
from a sample after bombardment with monoenergetic x-rays.
The orbitals of origin of the ejected electrons determine
their energies, with each element having characteristic
orbital ionization potentials. Thus, comparison of a
sample's ejected electron energy spectrum to known spectra
usually provides surface analysis and/or molecular structure
information. Since x-rays can eject electrons from at most
the top 100 Angstroms of a solid, ESCA is well suited for
surface studies. The applications of this method to a few of
the systems studied here will be discussed in the following
sections, and data given which may justify its even wider use
in future work.
Results and Discussion
Synthesis of a Salen Ligand on Silica Gel
The synthesis of a multidentate ligand system on a
rigid support such as silica gel was derived as a method for
possibly achieving properties different than its homogeneous
analogs. The ligand described here is a three nitrogen, two
oxygen donor which had to be synthesized stepwise on the
silica surface. The plain silica surface was first reacted
with (H^CO)3SiCH2CH2-(CgH4)-CH2C1 in order to produce the
chloromethyl functionality on the surface. In fact the

95
chloromethyl moiety attached to phenyl groups is similar to
the surface of polystyrene. Earlier work in this research
group led to the successful support of the desired ligand on
8 3
polystyrene. However, this polymer was not rigid enough to
produce all of the desired characteristics (vida infra). The
next step in the ligand synthesis is to react the chloro¬
methyl groups with HN(CH2CH2CN)2 (3,3'-iminodipropio-
nitrile) which will be referred to by its common name
dicyanoethylamine, DCEA. This reaction does not proceed
under routine conditions of mixing the DCEA with silica gel
in a solvent under nitrogen. Attempts to react DCEA with
chloromethylated silica gel under a normal inert atmosphere
leads to the polymerization of the DCEA into a viscous mass
accompanied by little DCEA incorporation. Experiments were
performed under high argon pressures after concluding that
rigorous exclusion of oxygen might be necessary. It was also
discovered that Alum and coworkers50 had reacted the chloro-
propyl group bound to silica gel with diethylamine at
elevated argon pressures to produce the bound tertiary amine.
Reaction of the silica gel with pure DCEA (without solvent)
in a pressure bottle of the type used for catalysis under 100
psi of argon pressure produced the DCEA bound to silica gel
as shown below.
[SG]-CH2C1 + HN(CH2CH2CN) 2 H-
[SG ]-CH2-N(CH2CH2CN)2 + HCl
(18)

96
Next, the cyano groups are reduced to amine
functionalities by reaction with B^H^/THF solutions under
nitrogen. This supported ligand is referred to as [SG]-DPT
from the common name dipropyltriamine (DPT). The general
scheme for the preparation of [SG]-DPT is shown in Figure 17.
Finally, the Schiff base condensation of [sg]-DPT with
salicylaldehyde is conducted in order to produce the desired
[SG]-SalDPT as shown in Figure 18. This supported ligand is
stable in air and the entire silica gel support is pale
yellow in color. Thorough washing, Soxhlet extraction and
complete drying of the silica gel after each step in this
procedure is very important. The [SG]-SalDPT was also
prepared with alkylation of the non-reacted surface silanol
groups, as were samples which varied in surface
concentrations of the -SalDPT ligand. A slight variation of
the ligand was synthesized using 3,5-dibromosalicylaldehyde
to produce [SG ]-BrSalDPT.
Characterization of these supported ligands is not
easily attained. The low loadings on the surface often rule
out the use of elemental analyses. The best method available
routinely is that of incorporating certain metals into the
silica bound ligand and comparing their electron spin
resonance (ESR) spectra to the spectra of their homogeneous
and polystyrene bound analogs. The [SG ]-DPT ligand when
stirred with copper(II) acetate in DMF binds the metal ion to
form [SGj-Cu(II)DPT which is green in color. Similarly,
[SG ]-Co(II)SalDPT is easily formed by mixing of the silica

Figure 17.
General scheme for the preparation of
[ SG ]-DPT.

98
HN(CH,CHXN).
ch2ci
CH,
CH,
NH.
BH /THF
— >
CH,
SG,
CH2N
- DPT
CH2
CH,
CH

Figure 18.
The preparation of [SG ]-SalDPT from [SG]-DPT.

100

101
gel supported SalDPT ligand with cobalt(II) acetate in DMF
solution. The ESR spectra of these complexes can then be
used for characterization to verify that the silica gel
supported species have been prepared. The oxygen adduct,
[SG ]-Co(II)SalDPT-02, must be used in order to obtain a
spectrum for the cobalt system. The ESR spectra of these
silica gel bound complexed are then almost identical to the
8 3
spectra of the polystyrene bound complexes. The attainment
of a stable multidentate ligand which is covalently bound to
a rigid silica gel support with site separation achieved by
surface alkylation is a development which has many possible
applications, several of which will be discussed in the
following sections.
Oxygen Transfer Using [SG ]-Fe( III) SalDPT and [SG ]-
Mn(II)SalDPT
Among the general interest in cytochrome P450
oxidations has been specific interest in aromatic and
aliphatic hydroxylations, alkene epoxidation, and interest in
the nature of the active oxidant. As mentioned previously,
most of the systems used to investigate these processes
involve iron or manganese tetraphenylporphyrin
7 2-7 8
complexes. Since silica gel supported iron(III) and
manganese(11) complexes can be easily prepared from the [SG]
-SalDPT ligand, these complexes were employed to determine

102
whether they could provide a polymer bound model for any of
the above reactivity.
Pressurizing the silica gel supported iron or manganese
complexes with dioxygen at 60 psi C>2 and 40°C in methanol
produced no oxidation of a cyclohexene substrate. This was
not surprising, however, since other oxygen sources are
usually required when examining the cytochrome P450 systems.
Iodosylbenzene, commonly used, is the oxygen source for all
of the results which follow.
Cyclohexene was employed as a substrate in order to
investigate epoxidation and hydroxylation of alkenes.
Cyclohexene, iodosylbenzene, and a cyclopentanone internal
standard were used in methylene chloride solvent along with a
polymer supported metal complex. Product formation was
determined by use of gas-liquid chromatography, using a
carbowax column at 130°C. The retention times varied with
fluctuations in gas flow, but the approximate average
retention times (in minutes) were the following: 0.8 for
CH2C12, 2.6 for cyclohexene oxide, and 8.7 for cyclohexenol.
The iron(III) complex, [SG]-Fe(III)SalDPT, converted
cyclohexene to cyclohex-2-enol and cyclohexene oxide, along
with producing iodobenzene from the iodosylbenzene in CH2C12
at room temperature. The general reaction using
[SG ]-FeSalDPT or [SG ]-MnSalDPT is represented in Figure 19.
This supported iron complex achieved oxygen transfer, but
also produced an interesting product distribution. Using a
homogeneous solution of tetraphenylporphinatoiron(III)

Figure 19.
General conversion of cyclohexene to corresponding
products in the presence of iodosylbenzene and a
supported metal complex.

(0)-Fe Sal DPT 10 OH I
or + O + CH2C'2> 0O + ó + CS)
(SG>MnSalDPT
104

105
chloride (FelIITPPCl) Groves et al. reported'5 production of
cyclohexene oxide and cyclohexenol in a ratio of 3.7:1 in
CH2C12 at room temperature. The silica gel supported
iron(III) produces cyclohexenol almost exclusively, with only
trace amounts of cyclohexene oxide formed. The homogeneous
system produces 4.2 total turnovers (based on mmol products
and mmol metal complex) in the relatively short time period
of 1-2 hours.75 The supported system reacts more slowly,
requiring 47 hours to produce 2.4 turnovers of the
cyclohexenol product. Also, commonly cited75 is the
destruction of catalyst by iodosylbenzene. This process does
not appear to occur to the silica gel bound complexes, in
that there is no color loss from the support into solution
and the [SG]-FeIIISalDPT resin when re-used several times
produces identical results each time in terms of the amount
of product formed and the rate of product formation.
The silica supported manganese complex, [SG ]-MnSalDPT,
also converts cyclohexene to cyclohexenol and cyclohexene
oxide. In this system, however, only cyclohexene oxide is
produced for the first 30-45 hours after iodosylbenzene
addition. Cyclohexenol is then produced relatively quickly
until the cyclohexenol to cyclohexene oxide ratio is 1.3:1
after approximately 53 hours of reaction. The supported
system yields 1.4 turnovers of exclusively cyclohexene oxide
by the end of 45 hours, but after 53 hours has produced 2.1
turnovers of the cyclohexene oxide product and 2.7 turnovers
of the cyclohexenol product. The supported Mn(II) system's

106
reactions were conducted under a nitrogen atmosphere. The
re-use of [SG]-MnSalDPT samples indicated the activity of the
used silica gel and showed no evidence of color loss into
solution. The yield of products was only monitored
approximately every 12 hours during re-use, but indicated the
same 1.3:1 product ratio of cyclohexenol to cyclohexene oxide
produced at approximately the same rate as the original
reaction had during its last hours. Cyclohexane is not
oxidized by either the supported iron or manganese systems
under the conditions used for cyclohexene oxidation.
A product of the reaction of ClMn(III)TPP derivatives
with iodosylbenzene is [CIMn(IV)TPP(OlPh)]^0, which is
capable of oxidizing alkane and alkene substrates at room
84
temperature under an inert atmosphere. Reaction of the
manganese dimer above with cyclohexene produces the following
oxidation products in one hour: 3-chlorocyclohexene, 32%;
cyclohexenol, 7%; cyclohexene oxide, 31%; 2-cyclohexen-l-one,
1% (percents based on three oxidizing equivalents for the
dimer). The incorporation of chloride into a product, along
with the relatively small production of cyclohexenol, are
results which differ from those of the silica gel supported
system. Both the homogeneous iron and manganese TPP
complexes yield products which contain anions which have been
incorporated from the TPP complexes. Obviously, the lack of
anions from the supported metal complexes excludes the
possibility of formation of any analogous products by the
supported systems.

107
In conclusion, the product distributions and lack of
catalyst degradation make the silica gel supported SalDPT
iron and manganese complexes, despite their slower rate of
activity, both interesting and worthy of further
investigations. Future adjustment of metal complex
concentrations or reaction conditions might provide progress
toward activation of alkanes by these heterogeneous
catalysts.
Synthesis of fSG1 -Fe(II)SalDPT
Complexes of iron(II) are of great interest, although
they are generally difficult to prepare as air stable
compounds. Previous attempts to prepare crystalline Fe(II)-
SalDPT resulted in irreversible oxidation presumably to the
oxo-bridged dimer. Preparation of Fe(II)SalDPT immobilized
on a rigid silica gel support was desired in order to compare
its properties to those of the attempted crystalline analogs.
Great care must be used to eliminate oxygen when
preparing the supported iron(II) complex. Performing cycles
of a freeze-pump-thawing procedure on [SG]-SalDPT in DMF
solvent is the best way to exclude oxygen initially. The
compound Fe(CO),. is employed as the source of iron and is
reacted with the silica gel supported ligand in Schlenk-type
apparatus. After reaction, filtering and thorough washing
(see Experimental Section) a purple/pink silica gel results.
This silica gel is very different in appearance from the [SG]
-Fe(IIDSalDPT complex which is a tan/brown color. Samples

108
of [SG]-SalDPT with 80% of its surface methylated (covered
with -Si(CH ^^ groups) and 0.05 mmol ligand per gram [SG] (1
ligand/20 surface Si) were used to prepare the iron(II)
complex in order to provide a surface which should have site
isolation of the iron centers (see Chapter III for details of
the alkylation process). The SalDPT ligand is attached to a
longer chain of atoms, and occupies a larger area, than the
sulfide ligand ([SG]-SH) discussed in Chapter III. As a
result, it is theoretically able to cover a greater area (780
2 .
A ) than the sulfide ligand and therefore requires a loading
of 1 ligand/18 surface SiOH or more dilute in order to
achieve site isolation. This is the loading necessary to
avoid any contact between ligands; however, alkylation of the
silica surface very likely allows site isolation at higher
ligand loadings. The larger steric bulk of the multidentate
ligand may also allow some amount of ligand-ligand contact
without the corresponding metal center interaction.
Mossbauer spectroscopy was used to help determine the
8 5
oxidation states of iron in silica gel supported species.
Spectra of supported complexes prepared with Fe(III) give
data indicative of an Fe(III) complex. The spectra are not
very intense or sharp due to the relatively low loading of
iron used to obtain site isolation coupled with the fact that
only the 2% abundant ^7Fe isotope of iron is Mossbauer
active. The silica gel supported Fe(III) complex yields
Mossbauer spectra very close to those reported for similar
8 3
polystyrene bound Fe(III) complexes.

109
The Mossbauer spectrum of a small [SG]-Fe(II)SalDPT
sample sealed under nitrogen was not intense enough to
provide a meaningful characterization.
The goal of preparing the [SG]-Fe(II)SalDPT complex was
to obtain site isolation of the iron centers and thus remove
the possibility of forming any type of oxo-bridged dimer
when exposed to oxygen. However, the supported iron(II)
silica gel turns from its original pink color to the tan
color of supported iron(III) within minutes upon exposure to
air. This change is non-reversible by treatment with vacuum
and the change also occurs at liquid nitrogen temperatures,
although more slowly. Due to the rigid nature of the silica
gel structure and the presence of surface methyl groups, it
seems unlikely that neighboring iron centers are able to
contact one another or to form oxo-bridged species. The
preparation of supported iron(II) complexes with even lower
surface concentrations of iron would be of interest to help
confirm that neighboring iron centers are not interacting.
Silica gel loadings of 1 ligand/50 surface Si (0.05 mmol
ligand/g [SG]) or even 1 ligand/100 surface Si (0.01 mmol
ligand/g [SG]) would be worthy of investigation. At such low
concentrations it would be difficult to obtain Mossbauer
spectra, so the distinct color change observed upon oxidation
from iron(II) to iron(III) would be the most convenient
method of determining whether that oxidation is occurring
upon exposure of the [SG]-Fe(II)SalDPT to air. Even at low
metal complex surface concentrations, the purple/pink

110
iron(II) color and the tan/brown iron(III) color should be
readily distinguishable on the silica gel.
The preparation and characterization of an iron(II)-
multidentate complex supported on a rigid inorganic polymer,
silica gel, has been accomplished. The possibility of
achieving reversible C>2 binding may be reached by this system
with further "fine-tuning" of the surface. Application of
the rather detailed information of the silica surface and of
effects of surface modification described in Chapter III
should be of use in future studies of this iron(II) system.
Incorporation of an Active Metal into a Functionalized
Support
The design of polymeric supports and of ligands to
immobilize catalytic species has been discussed and
demonstrated in earlier sections. A logical extension of
this concept is to incorporate one metal of a bimetallic
catalytic system into the support material while retaining
the ability to functionalize the support leading to the
immobilization of a second metal species on the support
surface.
2 5 2 6
The Wacker process ' referred to in Chapter II is a
well-known bimetallic system utilizing copper and palladium
complexes. The general mechanism for this process is shown
in Figure 20. The Mimoun system discussed at length in
Chapters I and II is a bimetallic system using copper and
rhodium complexes. Interest in these two systems was the

Figure 20.
General catalytic cycle for the Wacker
process.

112

113
primary justification to attempt to incorporate Cu(II) ions
into silica gel.
Copper(II) ions when mixed with plain silica gel in
water have no reaction with the silica surface. However,
silica gel treated with dilute aqueous hydroxide solution,
which is then thoroughly rinsed with water, reacts with
aqueous Cu(NO-j)2 to produce enough copper(II) on the surface
to give the entire silica gel a pale blue color. The
hydroxide solution presumably ensures that the silica surface
reaches its maximum concentration of surface -SiO Na+ groups.
When the hydroxide treated silica gel is mixed with excess
Cu(NO^)2, most of the copper ions do not stay on the silica
gel, but enough react to give the gel a very distinct blue
color. Techniques were later used to estimate the amount of
copper on the surface (vide infra). However, extensive
Soxhlet extraction of the silica gel with boiling water does
not remove copper ions, confirming that the copper is well
bound to the surface.
Silica gel was prepared with an anion exchange
capability with general formula [SG] -OSi(CH2CH2CH2)N(CH^)^I.
Details of these types of silica gels and their preparation
will be discussed in a later section. These samples can then
be rinsed with hydroxide and treated with copper(II) ions.
The typical blue copper color is then evident in the
resulting gel. The fact that some of the iodide ions on the
silica gel surface may be replaced by hydroxide ions during
this procedure does not matter in this application. The

114
anion exchange silica gel with copper ions incorporated is
then able to react with I^PdCl^ producing a green silica gel
with tetrachloropalladate ions exchanged onto the surface.
Homogeneous palladium(II)/copper(II) Wacker oxidations
were conducted using 1-hexene substrate yielding 2-hexanone
product. The homogeneous reaction was conducted at 70°C, 40
psi C>2 in an aqueous DMF solvent with 0.06 mmol of both
metals producing approximately 30 turnovers in 24 hours. The
heterogeneous oxidation was then conducted using the silica
24-
gel with Cu on its surface and palladium bound to it. The
conditions used were equivalent to those for the homogeneous
reaction, with approximately 0.07 mmol of palladium supported
on the silica gel. It is difficult to estimate the amount of
copper on the surface, it being the amount which is bound
after the surface is treated with NaOH. This heterogeneous
catalyst produced roughly 0.5 turnovers initially and then
did not yield any further product over a long time period.
There was no visible change to the silica gel catalyst.
The initial activity of the silica gel supported
catalysts is a positive result. Leaching experiments
indicate no activity in solution, so that any activity
observed is due to metals supported on the surface. One
possible factor limiting activity is that the palladium
complex is at the end of a relatively long chain of atoms
which bind it to the silica surface, while the copper ions
are located on the silica surface. The physical separation
between palladium and copper may well limit long term

115
catalytic activity. Normally one would predict that lack of
Pd/Cu contact would result in the production of reduced
metallic palladium and an accompanying grey/black color
change. In this case it is uncertain whether such a color
change would be visible due to the loading of the surface
with blue copper ions, and the low concentration (one
palladium ion per every 75 surface silanol groups) of surface
palladium. In this case, rather than site isolation, higher
surface loadings may improve activity.
Electron spectroscopy for chemical analysis (ESCA) was
employed to provide some information about the functionalized
silica surface. This work was done at the Major Analytical
Instrumentation Center (MAIC) of the University of Florida
through the assistance of Susan Hofmeister. The x-ray
photoelectron spectra resulting from a study of the Pd/Cu
silica supported system described above indicate the presence
of very small amounts of copper. Although ESCA is not a
precisely quantitative method, it does indicate the relative
amounts of species on a solid's surface. Since ESCA can
examine at the most a depth of 100 Angstroms on a surface,
this result would tend to indicate, despite the definite blue
color of the silica gel, a relatively low loading of copper
on the silica surface. This led to attempts to incorporate
copper ions into silica gel (vide infra) and suggested that
increased loadings of palladium may also be needed.

116
Apparently low loadings of copper ions on the silica
gel surface led to attempts to produce silica gel having
copper incorporated throughout the silica structure. The
approach taken was that of dissolving the silica gel and then
reforming the solid with copper ions interspersed in the
silica gel. The technique of dissolving silica gel in acid
(HC1), adding CutNO^)^» and neutralizing with base (NaOH)
produces a very blue silica gel which does not change after
extensive aqueous washings and extractions. The drawback to
the copper incorporated silica gel produced is that it
surface area is very much lower than that of the initial
reactant silica gel. All of the experiments conducted
support the validity of the chemical principles utilized in
this approach. However, in discussions with chemists from
W. R. Grace (manufacturers of Davison brand silica gel) the
rather sophisticated technology involved in production of
8 6
high surface area silica gel was revealed. It is uncertain
whether conditions sufficient to produce high surface area
silica gel can be obtained with materials available at a
typical academic laboratory. Industrial collaboration may be
worthwhile in order to produce a high surface area silica gel
with a metal ion incorporated into the silica gel matrix.
Surface functionalization in the usual manner should then be
possible ultimately yielding a bimetallic system with both
metals in and on a solid heterogeneous catalyst.

117
Synthesis of a Silica Gel Anion Exchange Resin
Anion exchange resins are commercially available
through several companies. However, they are virtually all
composed of polystyrene or other similar organic polymers.
The drawbacks to these substances are their lack of rigidity
and their inability to tolerate increased temperatures.
Polystyrene itself begins to soften at 85°C, and also has
solvent dependent swelling properties.
An anion exchange capability on silica gel was prepared
by first putting an amine moiety on the surface. The surface
is also covered with -Si(CH^)^ groups in order to achieve
site isolation of the other groups and in order to help
protect the surface 0-Si bonds of the functional groups from
hydrolysis. The amine groups are then reacted with
chloromethane in order to produce quaternary ammonium
chloride functionality on the surface. The analogous
quaternary ammonium iodide silica gel can be prepared by
reacting iodomethane with the supported amine.
The silica gel anion exchange resin reacted as would be
predicted in all of the applications in which it was used.
2-
The gel picked up PdCl4 ions as described previously. The
functionalized silica gel was shipped to the Sybron
Corporation where testing is being conducted to determine how
well this substance meets industrial criteria for a good
anion exchange resin. Initial results appeared encouraging,
but final results have not been reported.

118
The surface loading on the silica may be easily varied
to accommodate different applications. Lower loadings would
allow site isolation of species such as metal complex, while
higher loadings would of course provide the capacity to bind
larger quantities of an anion from solution. Silica gels of
several loadings were prepared. Due to the nature of silica
gel, each sample is independent of swelling problems and is
stable at much high temperatures than polystyrene resins.
Titanium Carbide as a Solid Support
The stability of any substance bound to a solid support
is ultimately related to the strength of the bond from the
surface of the support to the species attached to that
surface. The presumption that bonds of carbon or carbanions
to metal centers might be significantly stable led to an
investigation of titanium carbide (TiC) as a support
material.
Titanium carbide is very unreactive and so initial
attempts were made to alter the surface in order to generate
active surface species. Halogenation of the surface was
attempted by the passing of chlorine gas over TiC contained
in a tube furnace. Temperature of 150°C - 350°C during
exposure produced liquid TiCl4 along with black TiC of
unknown surface composition. Gradual heating up to 150°C
yielded no TiCl4 liquid.
Based on an estimation of the very small particle size
of titanium carbide, it is calculated that even complete

119
chlorination of the surface would yield a very small percent
of chlorine by weight which could not be measured by any
normal elemental analysis technique. Thus, it is difficult
to determine whether any chlorine atoms have been bound to
the carbide surface after treatment with chlorine. Several
unsuccessful attempts were made to react other species with
the alleged surface chlorides. The stirring of n-butyl
lithium in hexanes with chlorinated TiC, followed by addition
of the Rh(C0)2+ cation in THF was an attempt to place an
active metal center on the carbide surface. However, the
resultant solid was inactive for the oxidation of 1-hexene
with copper(II) added into solution under pressure (40
psi) at 70°C in ethanol solvent. As discussed earlier
(Chapter III), rhodium centers supported on silica gel under
similar conditions successfully oxidize 1-hexene to
exclusively 2-hexanone. Attempts to hydrogenate 1-hexene (as
solvent) under 50 psi H2 pressure at 45°C by the same
"TiC-Rh(CO)2" solid were also unsuccessful. The chlorinated
titanium carbide was stirred in a nitrobenzene solution
saturated with ammonia in an attempt to attach an -NH2
functionality to the carbide surface. No adequate technique
was found to quantitate the small amount, if any, of surface
amine produced. Attempts to titrate the surface amine with
acid were also unsucccesful. Liquid bromine was stirred with
plain titanium carbide in an effort to achieve bromination,
rather than chlorination, of the carbide surface. Here
again, the problem faced was that of determining the exent of

120
reaction that had occurred. Each of the approaches tried
with the chlorinated carbide was also used with the
brominated samples, producing equally unsuccessful results.
It was decided that more detailed knowledge of the
carbide surface is required to aid future attempts at
functionalization. As a result, ESCA studies of the plain
titanium carbide surface were conducted indicating at least
two different types of surface titanium atoms and more than
one type of surface carbon species. The overall ESCA
spectrum of titanium carbide is shown in Figure 21. An
expanded version of the carbon region of the spectrum reveals
two different types of carbon present and is represented in
Figure 22. The peak on the left represents carbon atoms
which are bound to oxygen or other carbon atoms, while the
peak on the right represents carbon atoms bound to titanium.
The titanium region of the ESCA spectrum shown in Figure 23
reveals at least two different types of titanium species
present. The ESCA technique provides a general indication of
relative amounts of surface species measured. Thus, all
further surface reactions on the carbide support should be
monitored by ESCA methods to determine the type and quantity
of resultant surface species. Other methods which yield more
accurate quantitative data are also available at the Major
Analytical Instrumentation Center, and these may also be
employed as needed.

Figure 21.
ESCA spectrum of titanium carbide (TiC) shown as
intensity (I) versus binding energy (B.E.).

2000
I
1000
0

Figure 22.
Carbon region of the ESCA spectrum of Tic.

285
B.E.
288
124

Figure 23. Titanium region of the ESCA spectrum of TiC.

470
460
B.E.
450
440
126

127
Fenton Chemistry
The conversion of isopropanol to acetone and 1,2-
propanediol is one example of the so-called Fenton
8 0
chemistry. This conversion was accomplished by aqueous
solutions of either FeCl2-4H2 temperature in the presence of aqueous 0.1 N HC104 and
hydrogen peroxide. Attempts were made to use [SG]
-Fe(III)SalDPT as a heterogenous model to achieve the same
reactivity. However, leaching of the iron complex off of the
silica gel support occurs under reaction conditions identical
to those described above. The silica gel completely loses
its brown color and a white gel is produced. Addition of
hydroxide ion to the colorless filtrate after reaction
produces a rust colored precipitate, presumably an iron oxide
compound. The silica gel supported iron(III) complex is the
presence of all starting materials except H2C>2 does not
completely leach into solution, as a pale brown color remains
on the gel. Hydroxide ion again confirms the presence of
iron in solution. It seems that leaching by acid alone is
not as complete as the metal loss in the presence of both
acid and hydrogen peroxide. The estimation of leaching was
based simply on the color changes involved, primarily loss of
color from the silica gel. If the amounts of leaching had
been small, some attempt would have been made to quantitate
the amount of iron leached into solution. However, in all of
the cases studied the amounts of leaching were quite large.

128
The use of pure isopropanol and of several different
isopropanol/water mixtures as solvents, as well as
acetonitrile solvent, produced no observable reduction in loss
of iron complex from the silica surface. The silica gel
samples tested had all of their available surface covered
with trimethylsilyl groups in an unsuccessful attempt to
protect the surface functional groups from hydrolysis under
these conditions. Systems which require the use of acid and
hydrogen peroxide are seemingly going to be very difficult to
catalyze by silica gel supported species. It is not known
whether any other surface groups would be able to better
protect silica supported functional groups under similar
conditions.
Experimental
Silica Gel
Silica gel employed in all of the following experiments
is Davison Grade 62 silica gel from W. R. Grace. This silica
gel has a wide pore diameter of 14 nm, a specific area of
2 3
340 m , and a pore volume of 1.1 cm /g as stated on the label
of the container. Maximum surface reactivity of the silica
gel is achieved by washing the silica gel with dilute acid
(0.1 M HC1) followed by thorough drying at 100°C under
vacuum. The silica gel retains its very white color
throughout the above washing procedure.

129
Functionalization of Silica Gel with 1-trimethoxysilyl-
2-(p,m, chloromethylphenylethane)
The silane, ( H^CO) ^Si (Cf^Ci^C^H^C^Cl > ' was Purc*:iasc^
from Petrarch Systems, Inc. The acid washed silica gel,
30 g, was placed in a 500 mL round bottom flask fitted with a
condensor and argon inlet. Xylenes, 225 mL, were stirred
with the silica gel with argon bubbling in from a plastic
needle for 45 minutes to an hour. An addition funnel with
another 75 mL of xylenes solvent was degassed with argon from
a separate argon inlet simultaneously. The appropriate
amount of silane was syringed into the addition funnel, along
with chlorotrimethylsilane if alkylation of the silica
surface is also desired. The silanes are then added dropwise
to the silica <"t®1 slurry which has been heated to near reflux
under an argon atmosphere. After addition (1-2 hours) the
slurry is stirred at gentle reflux overnight.
The following day the silica gel is cooled, then
filtered in air and washed with xylenes, benzene and
methanol. The silica gel is then Soxhlet extracted for 24
hours with benzene. The gel is finally dried at 70-80°C
under vacuum. This functionalized silica gel will be
referred to as [SG j-PhCt^Cl.
Preparation of Silica Gel Bound 3,31-Iminodi-
propionitrile
The nitrile, HN (Ct^Ct^CN) 2 , was purchasd from Kodak. A
sample of [SG]PhCH2Cl (9-10 g) as described in the previous

130
section was placed in a Parr pressure bottle with 30-35 mL of
3,3'-iminodipropionitrile and a magnetic stirring bar. This
was attached to a pressure head identical to that used for
catalysis (see Chapter II) except for its attachment to an
argon cylinder. The silica gel slurry was purged 8 times
with 80 psi Ar, then set to 90 psi Ar and placed in a 90°C
oil bath for 24 hours. Vapor pressure of the nitrile causes
the pressure to increase, but is vented if necessary to keep
the total pressure at 100 psi.
After one day, the slurry is cooled and the argon
pressure removed. Placing 20-30 mL methanol into the
pressure bottle and letting stand for a short while
facilitates filtering, which is best done on a Buchner funnel
with filter paper rather than a fritted filter. The silica
gel is washed with methanol, benzene and then more methanol
followed by Soxhlet extraction for 24 hours with methanol.
The silica gel is then dried at 70-80°C under vacuum.
Preparation of Silica Gel Bound bis-(3-aminopropyl)-
amine |SG]-DPT
A sample of silica gel containing cyano groups on the
surface as described in the previous section was placed into
a 500 mL 3 neck round bottom flask with a stir bar. Cycles
of evacuation and filling were alternated, followed by
syringed addition of 1 M BH^/THF solution (200 mL for a 25 g
sample). If the silica gel sample used has not been
thoroughly dried of methanol, a bubbling borane-methanol

131
reaction will be observed upon BH^/THF addition. The silica
gel is stirred in the borane solution for 24 hours under a
nitrogen atmosphere. The slurry is then heated to near
reflux for 2 hours, allowed to cool followed by the addition
of enough methanol to destroy all of the excess borane. The
mixture is again heated to near reflux for 1-2 hours, cooled
and filtered in air.
Washing procedure on a polymer such as polystyrene
would entail treatment with acid while heating, washing and
then treatment with base. However, there is a fear of
hydrolyzing the functional groups off of a silica surface with
acid. As a result, THF and toluene were used to wash the
filtered silica gel. Dilute (0.1 M) HC1 in dioxane was then
used to briefly treat the silica gel, then washed, and
finally pyridine in dioxane stirred with the silica gel.
Finally, thorough washing with methanol was done followed by
drying at 50-60°C under vacuum. Later experiments indicated
that heating with 3 M HCl/dioxane probably does remove the
functional groups from the silica surface as indicated by its
inability to react with salicylaldehyde (the next step) or to
8 7
incorporate copper(II) ions.
Condensation of Salicylaldehyde with [SGj-DPT
Benzene is added to [SG] -DPT to make a slurry, followed
by addition of a large excess of salicylaldehyde and several
hours of stirring, although reaction occurs very quickly.

132
The slurry is also heated for an hour to insure complete
reaction. The product with salicylaldehyde incorporated,
[SG]-SalDPT, is washed with benzene and ethanol thoroughly,
and then dried under vacuum at 60°C. The product silica gel
is a bright yellow in color due to the yellow Schiff base.
Incorporation of Metal Ions into [SG]-SalDPT
Several metal ions are incorporated into the bound
[SG]-SalDPT ligand by stirring the functionalized silica gel
with a DMF solution of the metal ion. Iron(III) chloride in
1:1 (v:v) DMF/pyridine and cobalt(II) acetate in DMF are used
to prepare [SG]-Fe(III)SalDPT and [SG]-Co(II)SalDPT,
respectively. The cobalt(II) analog is prepared under argon,
but both Fe(III) and Co(II) analogs are air stable.
Copper(II) acetate in DMF is used with the [SG]-DPT ligand to
prepare the [SG]-Cu(II)DPT complex. In each case the silica
gel ligand and metal ion solution are stirred overnight,
filtered and thoroughly washed or Soxhlet extracted.
The [SG]-Cu(II)DPT and [SG]-Co(II)Sal DPT•0-, (oxygen
adduct) both give characteristic ESR spectra similar to those
of their homogeneous analogs.
Incorporation of Fe(II) into [SG]-SalDPT
The Fe(II) supported complex preparation procedure is
quite air sensitive, and much care must be employed to
exclude oxygen. Distilled DMF (3Ü mL) is added to 2.0 g [SG]
-SalDPT or [SG]-BrSalDPT and the slurry freeze-pump-thawed

133
many (at least five) times. This is seemingly the best way
to exclude oxygen from the initial silica gel ligand. The
source of iron is FeiCO)^, which is poured through glass
wooland then placed under a nitrogen atmosphere. The Fe(CO),.
(2 mL) is syringed into the silica gel slurry and stirred
overnight in the dark, under inert atmosphere. The next day
the slurry (deep red in color) is heated for 3-4 hours (not
to reflux). The slurry turns a deep purple color during
heating. The slurry is cooled, then filtered in a Schlenk
apparatus which has been attached to the round bottom flask
throughout reaction. The silica gel was washed with DMF,
then the entire apparatus was transferred into an inert
atmosphere glove box. Here the silica gel is washed with
DMF, THF and diethyl ether until clear filtrates are
obtained. The pink silica gel is then dried under vacuum for
24 hours, and stored in the inert atmosphere box. The colors
during preparation and of the final solid correspond to those
8 3
found from similiar work conducted on polystyrene.
8 8
Mossbauer simulations were done by program DMOSFIT with
nuclear energy levels calculated using spin Hamiltonian
calculated data points fitted to experimental data using the
8 9
non-linear least squares program DSTEPIT.
Incorporation of Cu(II) into the Silica Gel Matrix
Davison Grade 62 silica gel, washed with 1 M NaOH, and
then copious amounts of water, is stirred with a copper(II)
nitrate solution for 24 hours. The resulting blue silica gel

134
can then be Soxhlet extracted with boiling water for several
days without the appearance of any blue copper ions in the
extraction water. This procedure places copper ions on the
silica surface.
Silica gel is dissolved in concentrated hydrochloric
acid in the first step to incorporating copper ions into the
silica gel. Excess Cu(NO-j) ^ 3H20 is added to the solution
and stirred for several hours. The solution is then
neutralized to pH 7 with large amounts of NaOH solution.
Upon reaching a pH of 7, the green solution turns to cloudy
blue as solid is formed. After 2 hours the solid is filtered
and washed with copius amounts of water. This very bluesolid
is dried under vacuum to yield a rather brittle,
non-uniformly sized silica gel. This resulting silica gel
appears to have copper ions as part of its structure, but its
surface area has been greatly reduced as evidenced by the
large chunk-like nature of the resulting solid. Extensive
physical crushing of the solid produces irregularly shaped,
brittle pieces which do not approach the small homogeneous
grain-like nature of the original silica gel.
Preparation of Silica Gel Anion Exchange Resins
Plain silica gel is reacted with (CH^CH2Ü)^Si(CH2CH2-
CH2NH2) and ClSiiCH^) (if desired) in xylenes in the same
manner as was described earlier in preparing chloromethyl-
phenyl silica gel. The functionalizing silanes are added
from an addition funnel dropwise into a slurry of the silica

135
gel in xylenes which has been heated nearly to reflux. An
amount of 2.8 mL (12 mmol) or 28.0 mL (120 mmol) of the
aminosilane may be reacted with 60 grams of plain silica gel
to yield products having 0.2 mmol -NH2/g [SG] or 2.0 mmol
HN2/g [SG], respectively. Some amount of CISKCH^)^ may also
be added to react with a percentage of the remaining surface
silanol groups (11.7 mL to react with all of the remaining
-SiOH groups). After 24 hours of reaction, the silica gel is
cooled, filtered and washed with xylenes, ethanol and
benzene. Soxhlet extraction in benzene and the usual vacuum
drying follow.
The resultant silica gel is then stirred overnight at
room temperature with a DMF solution which has been saturated
with CH^Cl gas. Also added to the slurry is a small amount
of 2,6-dimethylpyridine (2,6-lutidine) to act as a proton
sponge. Filtering, washing with acetone and benzene, and
drying under vacuum produce a silica gel with a quaternary
ammonium chloride functionality bound to the surface. A
quaternary ammonium iodide functionality is produced in an
identical manner by substituting iodomethane for
chloromethane above. These silica gels are then able to
function as anion exchange resins.
Titanium Carbide as a Solid Support
Titanium carbide was purchased from Aldrich and used
without further purification. A tube furnace was used with a
quartz tube with a three-way stopcock at one end and a two-

136
way stopcock at the opposite site. Titanium carbide was
placed in the center of the tube and purged with nitrogen,
the outlet end being attached to a bubbler. Chlorine gas
from a lecture bottle was slowly passed over the carbide
solid as the tube was slowly heated to 125°C for two hours,
then heated to 150°C for another hour. Other experiments
where the solid is heated to 250°C (or 350°C) produces a
clear liquid which fumes vigorously upon exposure to air
characteristic of TiCl4> The black solid is filtered and
washed with toluene. Both of the products described above
were used in further reactions as chlorinated titanium
carbide. These samples were stirred in a nitrobenzene
solution saturated with NH^ in an attempt to produce amine
groups on the surface. The chlorinated samples were also
treated with n-butyl lithium in hexanes under argon, followed
by reaction with [Rh(CO)^(solvent) ] BF^ in THF in an attempt
to bind the rhodium complex to the carbide surface. As
described in the Results and Discussion Section, no adequate
technique was employed to determine the success of these
reactions.
Bromine was also reacted with titanium carbide in
attempts to produce bromine atoms bound to the carbide
surface. Liquid bromine was stirred with titanium carbide
for 24 hours and then thoroughly washed with toluene.
Soxhlet extraction is strongly recommended in these systems
to remove reactants from the solid. Reaction schemes similar

137
to those carried out on the chlorinated carbide samples were
also conducted on the brominated carbides.
Fenton Chemistry
The substances FeCl2-4H20 (0.240 g) and .50 mL aqueous
0.1N NC104 are mixed together and degassed with N2 into which
1.1 mL isopropanol (2-propanol) is syringed followed by 0.1
mL 30% H202> This mixture is stirred under N2, aliquots
withdrawn and examined by GLC (DEGA column, 100°C). The same
procedure is employed using FeCl^ as the iron source.
The materials 0.18 g [SGJ-Fe(III)SalDPT (0.5 mmol
ligand/g [SG]), 50 mL 0.1N HC1C>4, 1.1 mL isopropanol and 0.5
mL 30% H2C>2 were used for supported reactions. After 24
hours of reaction, both the silica gel and filtrate were
colorless. Addition of hydroxide ion to the filtrate
produced a rust colored precipitate.
Into large screw top vials were placed 0.1 g samples of
[ SG] -Fe (111) SalDPT, 5 mL of 0.1N HC1C>4 prepared in the
solvent of choice, and 0.0 to 0.5 mL of aqueous 30% H2C>2.
The choice of solvent (water, isopropanol, several water/-
isopropanol mixtures, acetonitrile) had very little effect on
the extent of leaching, at least within the limits of
comparing color change by eye. The acid-only systems showed
markedly less leaching than did the acid/peroxide samples.
The silica gel samples treated with both acid and peroxide
were either completely white or very slightly brown after 24
hours, showing complete or nearly complete loss of metal from
the silica support.

CHAPTER V
GENERAL CONCLUSION
Throughout the previous chapters, research which
involved the use of transition metal centers as oxidation
catalysts has been described. The importance of careful
characterization of the active catalytic species in a system
has been presented. Also demonstrated has been the need to
obtain detailed knowledge of the surface in preparing
immobilized, catalytically active species on an inorganic
polymer such as silica gel. Applications to several ligand
systems and transition metals were presented, and the
potential for further expansion of this research pointed out.
Specific, detailed chemical conclusions were presented
with each topic as it was discussed. Overall, the goal of
this work has been to provide some insight into the nature,
design, support, application and refinement of several
transition metal oxidation catalysts.
138

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BIOGRAPHICAL SKETCH
The author, David Chappel Pribich, was born in Detroit,
Michiaan, on February 15, 1957. He was raised in Royal Oak
with his sister, Jean, by Mr. and Mrs. Milan Pribich and
graduated from Kimball High School in June, 1975. He
attended the University of Michigan in Ann Arbor and
graduated with honors in April, 1979, with a Bachelor of
Science degree. He began graduate studies at the University
of Illinois in Urbana and moved to the University of Florida
in Gainesville with the chairman of his doctoral committee in
order to complete the requirements for his Ph.D. degree. On
July 30, 1983, the author was married to Susan Elizabeth
Alberti, daughter of Mr and Mrs. Guido A. Alberti. The
author began employment by acquiring a postdoctoral and
teaching position at the California State University in
Northridge, California.
145

I certify that
opinion it conforms
presentation and is
a dissertation for
I have read this study and that in
to acceptable standards of scholar
fully adequate, in scope and quali
the degree of Doctor of Philosophy.
my
iy
ty,
as
Russell S. Drlgo, Chairman
Professor of Chemistry
I certify that
opinion it conforms
presentation and is
a dissertation for
I have read this study and that in my
to acceptable standards of scholarly
fully adequate, in scope and quality,
the degree of Doctor of Philosophy.
as
ISl'Ut'H’'
David E. Richardson
Assistant Professor
of Chemistry
I certify that
opinion it conforms
presentation and is
a dissertation for
I have read this study and that in
to acceptable standards of scholar
fully adequate, in scope and quali
the degree of Doctor of Philosophy.
my
iy
ty,
as
of Chemistry

I certify that
opinion it conforms
presentation and is
a dissertation for
I have read this study and that in my
to acceptable standards of scholarly
fully adequate, in scope and quality,
the degree of Doctor of Philosophy.
as
John Q. Dorsey
Assistant Professor
of Chemistry
I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.
)~i. /—I-
Hal H. Rennert
Associate Professor of
Germanic and Slavic
Languages and
Literatures
This dissertation was submitted to the Graduate Faculty
of the Department of Chemistry in the College of Liberal Arts
and Sciences and to the Graduate School, and was accepted as
partial fulfillment of the requirements for the degree of
Doctor of Philosophy.
May, 1985
Dean, Graduate School

UNIVERSITY OF FLORIDA
3 1262 08554 1372

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