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Scope and limitations of the 1,2 rearrangement of alkyl groups from carbon to metals to generate carbene complexes

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Title:
Scope and limitations of the 1,2 rearrangement of alkyl groups from carbon to metals to generate carbene complexes
Creator:
Hanna, Paul K., 1956-
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English
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vii, 179 leaves : ill. ; 28 cm.

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Subjects / Keywords:
Carbenes ( jstor )
Carbon ( jstor )
Chlorides ( jstor )
Ethers ( jstor )
Flasks ( jstor )
Hexanes ( jstor )
Photolysis ( jstor )
Rhenium ( jstor )
Solvents ( jstor )
Thermal decomposition ( jstor )
Carbenes (Methylene compounds) ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Organometallic compounds ( lcsh )
Rearrangements (Chemistry) ( lcsh )
Rhenium ( lcsh )
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bibliography ( marcgt )
non-fiction ( marcgt )

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Thesis:
Thesis (PH. D.)--University of Florida, 1988.
Bibliography:
Includes bibliographical references.
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by Paul K. Hanna.

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University of Florida
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. C


SCOPE AND LIMITATIONS OF THE 1,2 REARRANGEMENT
OF ALKYL GROUPS FROM CARBON TO METALS
TO GENERATE CARBENE COMPLEXES
By
PAUL K. HANNA
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
1988
[HOF F LIBRARIES


ACKNOWLEDGEMENTS
I would like to thank William M. Jones for his
patience and help throughout the years.
I would like to thank the people in the lab for their
help and encouragement, especially Yngve Stenstrom,
Su-Min Oon, Wayne Chandler, Nick Conti, Donna Crowther,
Rhonda Trace, Jasson Patton and Laura Quinn.
I would like to thank those people outside the lab
for reminding me (often!) that there is always a light at
the end of the tunnel. There are too many of these
people to mention, but Ted Streleski is not the least of
them.
Finally, a very special thanks to Jeanne Pittari,
Paul Hanna, and Mary Hanna; I couldn't have done it
without them.
11


TABLE OF CONTENTS
ACKNOWLEDGEMENTS ii
ABSTRACT vi
CHAPTERS
1 INTRODUCTION 1
2 RHENIUM 9
3 IRON 104
4 CONCLUSION 129
5 EXPERIMENTAL 132
General Procedures 132
Preparation of 1-Methoxy-l-
thiophenylcyclopropane (51) 133
Preparation of 1-Methoxycyclopropane-
carboxylic acid(53) 134
Preparation of 1-Methoxycyclopropane-
carbonylchloride (47) 135
Preparation of Pentacarbonyl(1-methoxy-
cyclopropyl-1-carbonyl)rhenium(44) 136
Photolysis of Pentacarbonyl(1-methoxy-
cyclopropyl-l-carbonyl) rhenium (44) 137
iii


Preparation of 1-Bromo-l-ethoxy-
cyclopropane(65) 139
Preparation of 1-Ethoxy-l-trimethyl-
siloxycyclopropane(70) 140
Preparation of Bromotetracarbonyl-
(triphenylphosphine)rhenium(75) 141
Preparation of Methyltetracarbonyl-
(triphenylphosphine)rhenium(76) 142
Preparation of (1-Ethoxycyclopropyl)-
phenylmethanol(77) 143
Preparation of 1-Methoxycyclobutane-
carboxylic acid(86) 144
Preparation of Pentacarbony1(1-methoxy-
cyclobutyl-1-carbonyl)rhenium(78) 146
Photolysis of Pentacarbonyl(1-methoxy-
cyclobutyl-l-carbonyl)rhenium(78) 147
Preparation of cis-Triethylphosphine-
tetracarbonyl-l-carbonyl(1-methoxy-
cyclobutyl) rhenium (107) 150
Photolysis of cis-Triethylphosphine-
tetracarbonyl-l-carbonyl(1-methoxy-
cyclobutyl) rhenium (107) 151
Preparation of Cyclopropylcarbinol(126) 153
Preparation of Cyclobutanol(127) 154
Preparation of Cyclobutyl Tosylate(128) 155
Preparation of Cyclobutene Epoxide(123) 156
Preparation of 7-Bromobenzo-
cyclobutene (140) 158
Preparation of 7-Cyanobenzo-
cyclobutene (141) 159
Preparation of Benzocyclobutene-7-
carboxylic Acid(142) 160
IV


Preparation of Benzocyclobutene-7-
carbonyl chloride (14 3) 161
Preparation of Benzocyclobutene-7-
carbonylrheniumpentacarbonyl (135) 161
Preparation of benzocyclobutene-7-
rheniumpentacarbonyl(136) 163
Preparation of Benzocyclobutene-7-
methoxy-7-rheniumpentacarbonyl(130) 164
Thermolysis of Benzocyclobutene-7-
methoxy-7-rheniumpentacarbonyl (130) 166
Preparation of Dicarbonyl-(n5-cyclopenta-
dienyl) (propyl) iron (162) 167
Preparation of Dicarbonyl-(n^-cyclopenta-
dienyl)- 2-propenyliron tetra-
fluoroborate (163) 168
Preparation of Dicarbonyl(n5-cyclopenta-
dienyl)[2-(N,N-dimethylamino)prop
-1-yl ] iron (165) 169
Photolysis of Dicarbonyl(n5-cyclopenta-
dienyl)[2-(N,N-dimethylamino)prop-1-
yl]iron(165). Isolation and Character
ization of Carbene Complex 169 and Chelate
Complexes 170 171
REFERENCES 17 5
BIOGRAPHICAL SKETCH 179
V


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
SCOPE AND LIMITATIONS OF THE 1,2 REARRANGEMENT
OF ALKYL GROUPS FROM CARBON TO METALS
TO GENERATE CARBENE COMPLEXES
By
Paul K. Hanna
December 1988
Chairman: William M. Jones
Major Department: Chemistry
This research investigates the generality of the
rearrangement of alkyl groups from carbon to metal. This
rearrangement had previously been observed only when the
metal was iron and the alkyl group was part of a strained
ring. In this research, systems were synthesized which
contained rhenium instead of iron and an acyclic alkyl
group instead of a strained ring.
The first system synthesized was pentacarbonyl(1-
methoxycyclopropyl-l-carbonyl)rhenium (44). Thermolysis
of this compound in toluene resulted in a complex mixture
which did not contain the desired rearranged product.
Photolysis of 44 in benzene resulted in formation of
vi


Re2(CO)10 and the dimer of the organic acyl fragment,
compound 54. The analogous pentacarbonyl(1-methoxy-
cyclobutyl-l-carbonyl)rhenium (78) was synthesized.
Thermolysis in toluene resulted in a complex mixture
which did not contain the desired rearranged product.
The photolysis of 78 was studied mechanistically. It was
shown to be a radical reaction involving metal hydrides
which generates
methoxycyclobutane (88)
and
1-
methoxycyclobutene
(89)
in a 1:1 ratio
at
room
temperature in benzene.
Photolysis at -65C
forms 1-
methoxycyclobutanecarboxaldehyde (115) in addition.
The pentacarbonyl(7-methoxybenzocyclobutene)rhenium
system (130) was synthesized through the intermediacy of
pentacarbonyl(7-benzocyclobutenylidene)rhenium tetra-
fluoroborate (137). This is the first known cationic
rhenium pentacarbonyl carbene complex. Thermolysis of
130 resulted in formation of benzocyclobutenone and
pentacarbonyl(7-benzocyclobutene)rhenium (136) with an
activation energy of 21.1 kcal/mol and an entropy of
activation of -2.1 cal/mol-K. The acyclic iron system
dicarbonyl- (n5-cyclopent adienyl) [2 (N, N-dimethylamino) -
prop-l-yl]iron (165) was synthesized and photolyzed. The
desired rearranged product (169) was isolated as
indicated by spectroscopy and chemical reactivity.
vii


CHAPTER 1
INTRODUCTION
The area of research into the chemistry of
organotransition metal carbene complexes was given a
boost when C. P. Casey and T. J. Burkhardt showed for the
first time in 1974 that such a compound (1) could induce
metathesis.1 This was significant in that it allowed the
interconversion of alkenes. One could start with
relatively simple alkenes and transform them into more
complex ones in a single step.
CeHs
(CO)s
c6h5
1
The splitting up of alkenes and their recombination is
both interesting from a mechanistic point of view and
practical in that a variety of alkenes may be synthesized
easily such as 1,1 diphenylethylene (4) in the example
above.
During the course of a theoretical study on these
carbene complexes H. Berke and R. Hoffmann2 investigated
the 1,2 migration of a carbon from a carbon to a metal
1


2
resulting in the formation of a carbene complex. The
reaction they specifically studied was the manganese
tetracarbonyl ethyl complex (5) rearranging to the methyl
manganese tetracarbonyl methylidene complex (6). The
calculations predicted that the energy of activation
should be essentially the same as the energy difference
between the two molecules. This indicates that the
activation energy for the rearrangement is nearly zero.
co
oc M rv- CH2-CH3
/I
oc' CO
CH3 CO
1/
oc M n = CH2
/I
oc' CO
5
6
In contrast to this predicted facile rearrangement
there was until recently only one reported case in which
there was any evidence that an alkyl group migrated from
a carbon to a metal to generate a carbene complex.3 This
was a case in which the metal was Ni and the presumed
carbene complex (8) was unstable, its existence was
inferred from the resulting chemistry which involved the
trapping of the intermediate carbene (8) with cyclohexene
to generate the norcarane (9).


3
There are a great many processes which involve an
analogous rearrangement, the migration of hydrogen to the
metal center instead of carbon.4'5'6
CP2
10
-c2h4
cd3
+ /
Cp2W
11
D
+ /
Cp2W
12 ^CD2
PMe2Ph
PMe2Ph
Cp2W
\
cd3
11
PMe2Ph
D
Cp2W
XD2-PMe2Ph
D-.
(PPh3)3M -CH3 CD4 + CD3H + CD2H2 + CDH3 + CH4
15
M = Co, Rh
There are, however, many cases known in which an
alkyl group on a metal center migrates to a carbenic


4
carbon which is on the same metal. This results in the
destruction of the carbene center and the formation of a
new C-C bond.7'8'9
+/
Cp2W
\
ch3
CHs
-H
CHjCN
CpjW

ch2
V
c6h5
17
ch2c6h5
Cp2W
IS
CHjCN
+ CH2C6H5
Cpjv/
ncch3
15
I 3 PMe3
+ I /
Br I r CHp
' i
PMe3
Me3P
PMe3
+ /
BrI f- CH2-CH3
Me3p/F>Me3
20
21


5
ch3
ch2-ch3
CP2\
22 CH3
-H
/
Cp2W
23 CH3
24
+
A
Cp2W
\
H
25
All of these facts point to the conclusion that the
predicted facile equilibrium of Berke and Hoffmann2 is
not an equilibrium at all for carbon systems. The
rearrangement normally goes in the direction that leads
to the destruction of the carbene center. The reason for
this "one way equilibrium" has been postulated by N. J.
Cooper and M. L. H. Greene to be one of thermodynamics.3
In an organometallic system in which there is a vacant
coordination site on the metal such a migration is often
possible. When the migration of an alkyl group from a
carbon to a metal center occurs the net result is the
loss of a C-C bond, the formation of a M-C bond, and the
conversion of a M-C bond into a M=C bond. This change
was thought to be thermodynamically unfavorable. The
molecule would invariably find some other, more
energetically favorable, pathway to fill the vacant
coordination site. It is important to note that if this


6
theory is correct, the rearrangement of an alkyl group
from a carbon to a metal generating a carbene complex may
be brought about if the system is perturbed so that the
rearrangement is energetically favorable.
Chemists have long known that the way to shift the
position of an equilibrium is to change the thermodynamic
preference on one side relative to the other. One way to
do this is to decrease the energy of the less favored
side. The other is to increase the energy of the more
favored side.
Energy
While working towards a completely different goal,
Jim Lisko serendipitously employed both of these
techniques and discovered that the rearrangement of alkyl
groups from carbon to metal centers could not only be
made to occur, but to give a stable carbene complex
containing an organic ligand bonded to the metal
center.^


7
The organic ligand in the starting material contained a
cyclopropane ring (27), which expanded to a 5 membered
ring in the product (28). The ring strain of the
cyclopropane in effect raised the energy of the starting
material (27). A 5 membered ring,as is in the product
(28), is relatively unstrained and does not affect the
relative energies.11 The product (28) contained an
electron donating methoxy group on the carbene carbon.
These are known to stabilize12 carbene complexes of iron.
This, in effect, lowered the energy of the product. The
result of combining these two factors was that the
rearrangement occurred readily. This supported the
previous hypothesis of Cooper and Greene3 that
rearrangement normally does not occur because of
unfavorable thermodynamics.


8
A number of researchers undertook investigations to
delineate the scope of this rearrangement. The initial
efforts focused on a narrow area. The rearrangement was
only studied in systems containing iron bound to highly
strained rings with strongly electron donating groups in
the alpha position (29) and under photolytic
conditions.
N = 2.3
X = OR. NR,
The work that will be described here will be
investigations intended to generalize this rearrangement.
It will concern the efforts to initiate such a
rearrangement on a different metal center (which could
undergo the rearrangement thermally) and in an iron based
system in which the rearrangement might occur with no
ring strain in the starting material.


CHAPTER 2
RHENIUM
In an effort to extend this rearrangement to a
different metal system a thorough literature search was
undertaken. There were obviously a great number of
possibilities from which to choose a reasonable
combination of metal and ligands. This search resulted
in the choosing of the rhenium pentacarbonyl group as a
very promising metal system for this rearrangement.
There were a number of factors which helped in this
decision. The first was that rhenium is a third row
transition element. Third row transition elements are
known to form relatively strong single and double bonds
to carbon.12'14 This is generally attributed to their
larger d orbitals, the energies of which allow better
overlap with the carbon orbitals than the first row
elements are capable of. This increases the stability of
the resulting complexes. Indeed there are a wide variety
of stable rhenium acyl complexes (e.g. 31), alkyl
complexes (e.g. 32), and finally there are also carbene
complexes (e.g. 33).15'16'17
9


10
o
(COLRe
22
och3
(CO)4Re=^
ch3
Re(CO)5
21
It was believed that the existence of these closely
analogous complexes would presage the stability of the
complexes that this project would entail making.
The second factor that pointed to this system as the
system of choice was the fact that the rhenium
pentacarbonyl anion (35) is moderately nucleophilic.18
Relative
Nucleophilicity
Cp(CO)2Fe
+
R-X
PhS
+
R-X
(CO)5Re"
+
R-X
Cp(CO)3W"
+
R-X
(CO)5Mn
+
R-X
R = CH3I, C2H5I, C2H5Br,
Cp(CO)2 Fe-R
7xl07
PhS-R
2.6x10
(CO)5Re-R
2.5x10
Cp(CO)3w-r
5xl02
(CO)5Mn-R
7.7x10
(CH3)2CHBr


11
It was presumed that this would be advantageous during
the synthesis of starting materials. One possible
synthetic strategy would be to first make the appropriate
organic substrate, then attach the metallic fragment via
a nucleophilic substitution reaction.
The third factor was the ease of synthesis of the
rhenium-containing precursors of the desired
organometallic compounds. The rhenium pentacarbonyl
anion (35), for example, is synthesized by a simple
sodium amalgam reduction of commercially available
dirhenium decacarbonyl (34).^9
Re2(CO)10
34
Na/Hg
THF
+
2 Na Re(CO)s
21
This could then serve as a nucleophile for reaction with
an organic moiety containing a strained ring (36) that
would generate the organometallic complex 37. This would
later undergo the ring expanding rearrangement to
generate a carbene complex.


12
If one treats dirhenium decacarbonyl (34) with
iodine, one can easily obtain (CO)5ReI (39).20
CHC1,
Re;(CO)]0 + h ; 2(CO)5Re-I
,4 T&
In the reverse of the step mentioned above which
generated an organometallic complex (37) via nucleophilic
attack of the rhenium pentacarbonyl anion (35) on an
alkyl halide (36), this metal halide (39) could then be
attacked by an organic nucleophile (40) which contained
the strained ring, resulting in the generation of the
same sigma complex (37).
OCH,


13
Both of these methodologies arrive at the same types of
desired products, but from completely different
directions. Thus the choice of the rhenium pentacarbonyl
system provided a back up system for the formation of the
desired organometallic target compounds should our first
attempt fail.
The final factor which was in favor of the rhenium
pentacarbonyl system was the fact that the terminal
carbonyls are thermally labile. This is best exemplified
by the fact that one of the standard methods for forming
rhenium pentacarbonyl sigma complexes (e.g. 42) is
thermolysis of the corresponding acyl compounds (e.g.
(CO)5Re-CH3
42
The generally accepted mechanism for this transformation
involves initial dissociation of a terminal carbonyl
followed by migration of the alkyl group to the vacant
site on the metal center. The net result is the
conversion of an acyl complex (e.g. 41) into an alkyl


14
complex (e.g. 42) with the loss of one of the terminal
carbonyls.22
(CO)5Re-CH3
42
This is significant in that it provides a
thermal route to a vacant site on the metal center. In
the metal systems which were known to undergo the desired
rearrangement (e.g. the rearrangement of 29 to 30)
photolysis of the starting material was neccessary to
expel a CO and provide a vacant site for the
rearrangement. The thermal lability of the COs on the
rhenium pentacarbonyl system opens the possibility of
thermally initiating the desired rearrangement.
Whenever one is expanding one's area of knowledge,
the most rational approach in order to prevent utter
confusion is to change only one variable at a time and
see what effect it has. If this guideline is applied to
the attempt to search for a different metal system to
undergo the rearrangement, then it is obvious that the
organic fragment should be the same as one that is known


15
to rearrange in the original iron system. For this
reason it was decided to make pentacarbonyl(1-methoxy-
cyclopropyl)carbonylrhenium (44).
o
44
It was believed that this (44) could be either
thermolyzed or photolyzed to generate the sigma complex
(45). Upon further irradiation or heating this (45)
would undergo the desired rearrangement yielding the
carbene complex (46).
o
The synthesis of the starting acyl complex (44) was
accomplished without much difficulty. The basic plan was
to react the metal anion (35) with 1-methoxycyclopropane
carboxylic acid chloride (47).


16
This is the same pathway that was followed in the
original iron system (26). The (CO^Re- (35) was
synthesized easily in the fashion mentioned previously.
The synthesis of the acid chloride (47) was successful
although fairly time consuming. The starting material
was thiophenylcyclopropane (48), which was treated with
n-butyllithium to form the anion (49) and then I2 to form
the iodide (50).23
sc6h5
H
nBuLi
SC6H5
[X
sc6h5
X,
42
5Q
Treatment of this compound (50) with base (K2CO3) and
CH3OH converted the iodo substituted cyclopropane (50)
into a methoxy substituted compound (51).
¡X
sc6h5
5Q
k;co3
SC6Hs
och3
1
MeOH


17
The next step was the conversion of the thiophenyl group
into a carboxylic acid. This was accomplished by
reductive cleavage of the thiophenyl group of (51) with
lithium naphthalenide and then bubbling C02 into the
reaction mixture.23'24 The methoxycyclopropyl anion (52)
attacks the C02 to generate 1-methoxycyclopropane
carboxylic acid (53). The yields are generally low and
highly variable. The byproducts (thiophenol and
napthalene) have a wretched stench.
sc6h5
X
och3
1L
Li Nap
l)C02
co2h
IX
och3
THF
^OCH,
a
2) h3o+
When the product
(53) was obtained, however,
conversion
into the desired acid chloride (47) was easily effected
by treatment with oxalyl chloride. Purification was
accomplished by Kugelrohr distillation.


18
Finally, reaction of this acid chloride (47) with the
rhenium pentacarbonyl anion (35) gave the desired acyl
complex (44) in moderate yields (generally 40% 50%).
o o
The next step was the decarbonylation of the acyl complex
(44) to form the alkyl complex (45).
This was expected to be a simple step, but it turned out
to be the one that brought this pathway to a complete
stop. We were unable to generate the 1-
methoxycyclopropyl sigma complex (45) from the acyl


parts per million
Figure 1: -*-H NMR of Pentacarbony 1 (1-methoxycyclopropyl-
l-carbonyl)rhenium(4 4 )


parta par million
Figure 2: 13C NMR of Pentacarbonyl(1-methoxycyclopropyl-
1-carbonyl)rhenium(44)


o
Figure 3: IR of Pentacarbonyl(1-methoxycyclopropyl-l-
carbonyl)rhenium(44)


22
complex (44) synthesized above. Thermolysis in toluene
resulted in gross decomposition. There were a great many
products as shown by thin layer chromatography. All of
these products were in low yield and none could be
characterized adequately. We next turned our attention
to the photochemical decarbonylation of this acyl complex
(44). The photolysis in deuterobenzene was a very clean
reaction. There were only two products. These were
shown to be the dimers of the metallic fragment (34) and
the organic fragment (54).
The inorganic dimer (34) was characterized by TLC and
FTIR. The organic dimer (54) was characterized by
NMR, FTIR, and GC/MS.
These results indicate that the main productive
process is homolysis of the Re-C acyl bond in (44) and
subsequent dimerization of the radicals (55 and 56).


Figure 4: Photolysis of Pentacarbony1(1-methoxy-
cyclopropyl-1-carbonyl)rhenium(44)


o
o
Examination of this failure to decarbonylate shows
that it is not without precedent.15 There have been
references in the literature to other cyclopropyl acyl
complexes (57) that could not be decarbonylated to the
corresponding alkyl complexes.
M = CpFe(CO)2
(CO)5Re
(CO)5Mn


25
It is generally acknowledged25 that in photochemical
decarbonylations there are two competing processes: the
first is homolysis of the M C bond; the second is the
photoexcitation and subsequent dissociation of CO from
the metal center. It seems reasonable, therefore, that
if for some reason the migration of our
methoxycyclopropyl group to the metal were proceeding
either slowly or not at all, then the vacant site on the
metal center would have time to pick up a CO from
solution. This would regenerate the starting material
(44) and make the dissociation a non-productive process.
The homolysis to form the radicals 55 and 56 would be the
only observed process.
Further examination of the literature reveals that
the migration of a recalcitrant cyclopropane from an acyl
carbon to a metal center is highly solvent dependant. In
the iron case mentioned above the reaction was later
shown to go cleanly in acetone but only very poorly in
petroleum ether.26


26
The photolysis of the rhenium methoxycyclopropyl acyl
complex (44) was consequently tried in acetone. The
results were significantly different. The most obvious
result was that there were a large number of products.
Analysis of the volatiles by capillary gas chromatography
revealed 15 components. Product identification was
attempted by GC/MS. Unfortunately the poorer quality of
the separation on this instrument resulted in the
identification of only 5 of these components: 54, 60, 61,
62, and 63.


27
MeOH
61
The problem seemed to be that we were unable to form
the needed sigma complex (45) that could undergo the
rearrangement. The presence of the carbonyl-containing
compounds (54, 60, and 61) indicates that cleavage is
taking place before the alkyl group shifts to the metal
center. The presence of methoxycyclopropane (62) may be
explained in two ways. The first is that the sigma
complex (45) was formed and then decomposed via radicals


28
55 and 64. The second is that the acyl complex (44)
decomposed to an acyl radical (56) which then lost CO to
generate the methoxycyclopropyl radical (64) and then
picked up the H. We have no evidence to favor either of
these mechanisms.
(CO)5Re
55
O
ch3o
-CO
(CO)5Re
SI
XJ
ch3o
£4
Since we were unable to obtain the desired sigma
complex through decarbonylation, we decided to attempt to
avoid the intermediacy of the acyl complex (44) and
synthesize the sigma complex (45) directly. There were
two ways we could go about this. We could either use the
rhenium pentacarbonyl anion (35) as a nucleophile and


29
attack an appropriately substituted alkoxycyclopropane
(36 or 65) in the alpha position or we could use a
nucleophilic alkoxycyclopropyl anion (40 or 67) and
displace a leaving group from the rhenium (39).
(CO)sRe-
(CO)5Re
OEl
66
(CO)5Re-I
22
(CO)5Re
OEt
The sequence employing rhenium pentacarbonyl anion
(35) as a nucleophile was attempted first since the
reactions were more familiar and, in any event, the
organic reactant (65) would need to be synthesized anyway
for the sequence employing the cyclopropane (67) as a
nucleophile. It was realized that this sequence was not
on firm ground since the rhenium pentacarbonyl anion (35)
is only moderately nycleophilic18 and it would need to
attack a quaternary carbon.
Both the organic and inorganic reactants were
synthesized by literature procedures.19 The organic


30
synthesis first involved reduction and ring closure of
ethyl 3-bromopropionate (68) followed by trapping with
trimethylsilyl chloride to give 1-ethoxy-l-trimethyl-
siloxycyclopropane (70) in 57% yield.27
o Na x tmsci
Ei20 ^ OEt
This (70) was then treated with phosphorous tribromide to
generate 1-bromo-l-ethoxycyclopropane (65) in 72%
yield.28
OTMS
OEt
ZQ
OTMS
OEt
22
PBr3
As in the case of the acyl complex, the rhenium
pentacarbonyl anion (35) was generated by reduction of
commercially available Re2(CO) 10 (34) with sodium
amalgam.
The results of mixing the rhenium pentacarbonyl anion
(35) with 1-bromo-l-ethoxycyclopropane (65) were very


31
disappointing. After periods of time ranging up to two
days, the starting organic material (65) could be
recovered unchanged. The rhenium pentacarbonyl anion
(35) is somewhat unstable, eventually going to a variety
of inorganic compounds, as evidenced by TLC, IR, and 1H
NMR.
(CO)5Re-
21
ill
No Reaction
In order to verify that the problem lay with the reaction
and not something else, the reactants were tested
separately. Since we could easily make the cyclopropyl
acyl complex (44) we knew that we were making the metal
anion (35) correctly.
A co-worker reacted the 1-bromo-l-ethoxycyclopropane
(35) with the much more nucleophilic dicarbonyl(n5-
cyclopentadienyl)iron anion (71), the result being the
desired sigma complex (72) in 25% yield.28


32
The most likely cause for the lack of reaction, then, is
insufficient nucleophilicity of the rhenium pentacarbonyl
anion (35).
This failure was disappointing, although not entirely
surprising. We next turned our attention to the use of
the 1-ethoxycyclopropyl anion (67) as a nucleophile. The
syntheses of the reactants were again relatively simple.
Treatment of Re2(CO)10 (34) with I2 results in (CO)5Re-I
(39).Treatment of 1-bromo-l-ethoxycyclopropane (65)
with tert-butyllithium is known to give the metal
exchanged product (67).28 To our surprise, there was no
reaction when the two were mixed. The (CO)5Re-I (39)
could be recovered after reaction times of up to two
days.
(CO)sRe-I
22
No Reaction
A literature investigation indicated that (CO)5Re-I
(39) had not been the most favorable system to try this
reaction on. It has been shown that when CH3Li is mixed
with (CO)5Re-I (39) displacement of the iodide to give


33
the methyl sigma complex (42) does not occur. The
isolated product is the acetyl-iodo rhenium anion (73).20
CH3Li
(CO)5Re-I
12
CO O
I y>-CH3
OC ReI
Li+
OC
/
CO
21
Indeed, if two equivalents of methyllithium are added to
the same reagent (39) and then the product protonated,
the resulting compound is the bis hydroxycarbene (74).30
(CO)jRe-I
12
1) 2CH-.U
2) H+
CO 9H
l/CHj
OC ReI
/
OC
HO
24
The literature also reports that if one of the
terminal COs is replaced by a phosphine then the
substitution of the halide in 75 by a methyl group may be
accomplished easily to give 76.2-'-


34
CO
l/
OC Re Br
/ \
OC pph3
CH3Li
CO
I CO
I /
OC Re ch3
/ i
OC pph3
H
76
The phosphine substituted rhenium halide (75) was
synthesized according to literature procedures in 21%
yield (literature yield 52%).32
Br,
Re->(CO)10 (CO)5Re-Br
CC14
34
PPh3
CHClj
(PPh3)(CO)4Re-Br
11
The reaction with 1-lithio-l-ethoxycyclopropane (67) was
carried out. Unfortunately, the results were the same.
The starting rhenium reagent (75) could be recovered
unchanged after two days of reaction.
In order to rule out the possibility that the 1-
lithio-l-ethoxycyclopropane (67) was not being generated


35
at all, the same procedure that had been used previously
to generate it was performed and then benzaldehyde was
added. After protonation and work up the resulting
alcohol (77) was isolated in 67% yield.
11
At this point we were forced to abandon the choice of
cyclopropane as the strained ring to undergo
rearrangement. Our attempts to form the sigma complex
(66) directly were fruitless. Although we were
successful at forming the acyl complex (44), it would not
decarbonylate to form the sigma complex (45) or carbene
complex (46).
The most reasonable alternative to the cyclopropane
system was the cyclobutane system. The reaction scheme
we chose is shown below.


36
There were three reasons for this choice. The first is
that experiments with the analogous dicarbonyl(n5-
cyclopentadienyl)iron system (81) have shown that the
rearrangement of interest can occur in the cyclobutyl
system.13
The second reason was that it was hoped that the
cyclobutyl ring would migrate from the acyl carbon to the
iron to form a sigma complex more easily due to its more
normal ring bonds.
The last reason is that the necessary organic acyl
chloride (87) was known and may be made easily.13


37
co2h
M
DUDA
2) 02
3) NaHSOj
OH
CO2H
8S
NaH
CH3I
OCH3
co2h
o
<
SI
The synthesis of the starting
accomplished in 52% yield without
acyl complex
incident.
(78) was


o
ia
'll (C6I>6)
u>
en
parts per million
Figure 5: XH NMR of Pentacarbonyl(1-methoxycyclobutyl-
1-carbonyl)rhenium(78)


o
OCH-i
(COkRc
la
13C |1111 (UX I
X
X
1 1 1
w
&
300
250
100
Figure 6:
200 150
parts per million
13C NMR of Pentacarbonyl(1-methoxycyclobutyl-
1-carbonyl)rhenium(78)
50


Figure 7: IR of Pentacarbonyl(1-methoxycyclobutyl-l-
carbonyl)rhenium(78)
o


41
Upon thermolyis in toluene at 105C, however, the
reaction did not go as expected. Thermolysis yielded
several products, all in poor yield. The mixture of
products was very difficult to separate. After many
attempts at column chromatography we gave up trying to
purify the mixture. Some information, however, could be
gleaned from the results. The large amount of gas
evolution observed combined with the observation of peaks
in the vinylic region of the 1H NMR spectrum and the lack
of a characteristic peak very far downfield in the 13C
NMR spectrum indicate that a probable sequence involves
decarbonylation, formation of the desired sigma complex,
and then decomposition via eliminations and ring opening
reactions of the cyclobutane ring. The absence of the
peak far downfield in the 13C spectrum indicated that the
desired carbene complex (80) was not present within the
limits of detection. The 1H NMR spectrum did not
indicate the presence of either methoxycyclobutane (88)
or 1-methoxycyclobutene (89). After this we abandoned
hope of obtaining the carbene (80) via thermolysis. We
turned our attention to photolysis.
It was hoped that the reason for the decomposition
was the large amount of energy available at this high
temperature. It was believed that by doing the


42
decarbonylation photochemically at lower temperature the
sigma complex (79) would not have enough energy to
decompose as it had at higher temperature in the
thermolyses.
The results of the photolyses in deuterated benzene
indicated that these expectations were partially correct.
They indicate that the decarbonylation and rearrangement
to the sigma complex did take place successfully. It did
not react further in the same way that it had under
thermolytic conditions. Instead the sigma complex
reacted further in a very interesting and unexpected way.
The products obtained were characterized by NMR,
FT-IR, GC-MS, and comparison to the reported properties
of the known compounds.33,34 The organic products were
shown to be a nearly 1:1 mixture of methoxycyclobutane
(88) and 1-methoxycyclobutene (89) The inorganic
product was determined to be almost exclusively dirhenium
decacarbonyl (34).
Reo(CO)io
och3
+
£&
och3
M
8£


H
parts per million
Figure 8: Photolysis of Pentacarbonyl(1-methoxy-
cyclobutyl-1-carbonyl)rhenium(78)


44
There were two possible mechanisms that were
considered to explain this observation. They both start
with the decarbonylation of the acyl complex (78) and
subsequent rearrangement to the desired sigma complex
(79). The two mechanisms then diverge. The first
mechanism relies on beta hydrogen abstraction by the
metal to generate the products. The second relies on a
radical pathway to produce them.
The overall scheme of the beta hydride abstraction
mechanism is as follows:
och3
L(CO)4Re-H + |
21
£2
och3
(CO)4Re
22
och3
Re2(CO)10_nLn + p
och3
(CO)5Re-
-CO
och3
\
(CO)4Re
22
H
There are two variants of the radical process, a
chain mechanism and a non-chain mechanism. An overview
of the non-chain mechanism is as follows:


45
och3
V
M
och3
V
22
och3
(CO)5Re + X
52
I 2£
Re2(CO)10
24


46
The steps in the chain mechanism are very similar to
those in the non-chain mechanism:
och3
0CH3
(CO),
G
light
(CO)5Re
55.
79
21
och3
(CO)5Re-
22
(CO)5Re
51
£2
(CO)5Re-H
94
OCH3
v
(CO)5Re +
51 M


47
The first step in the beta hydride abstraction is
proposed to be dissociation of a CO from the sigma
complex (79) to form a 16e intermediate (95). This
intermediate could either pick up a ligand from solution
or abstract a beta hydrogen to give a methoxycyclobutene
pi complex containing a metal hydrogen bond (90 or 98).
och3
(CO)5Re
-CO
79
OCH3
(CO)4Re
25
och3
L(CO)4Re
26
och3
(CO)4Rc
H
20
och3
L(CO)3Re
22
och3
L(CO)3Re
H
28
This type of rearrangement has been shown to occur in the
analogous dicarbonyl(n5-cyclopentadienyl)iron system
(99).13


48
22
CO'
m
och3
The pi complex could then expel the 1-methoxycyclobutene
(89) and replace it with a ligand from solution to give a
hydride complex (91 or 103).
och3
V.
(CO)4Re [_
H
2Q
L L(CO)4Re-H
21
och3
V
£2
och3
L(CO)3Re
L L^CO^Re-H
m
och3
H
102
£2


49
This hydrido complex (91 or 103) would then attack a
molecule of 1-methoxycyclobutane sigma complex (104) to
generate methoxycyclobutane (88) and the metal dimer
(106).35
LM(CO)5.MRe-H +
21 M=1
103 M=2
OCH3
(CO^Re
104 N=4,5
OCH3
\1_
+ Re2(CO))0.MLM
fifi
The other mechanism involves the homolytic cleavage
of the acyl (78) or sigma complex (79) to generate the
rhenium pentacarbonyl radical (55) and the
methoxycyclobutyl radical (93). The rhenium
pentacarbonyl radical (55) could then abstract a hydrogen
from a molecule of the sigma complex (79) to generate
methoxycyclobutene (89), (CO)5Re-H (94), and another
rhenium pentacarbonyl radical (55).


50
OCHj
(CO)5Re
22
light
(CO)5Re
55
, och3
(CO)5Re
79
och3
/

22
och3
+
22
(CO)5Re +
55
och3
V
+
£2
(CO)5Re-H
24
In the non-chain mechanism the rhenium pentacarbonyl
radical (55) abstracts a hydrogen from the
methoxycyclobutyl radical (93) to generate the metal
hydride (94) and 1-methoxycyclobutene (89).
och3
(CO)5Re
22
light
(CO)5Re
55
+
och3
/
(CO)5Re-H
24
+
och3
\
£2
22


51
The hydride (94) could then react with another molecule
of the 1-methoxycyclobutyl sigma complex (104)36 or the
methoxycyclobutyl radical (93) to generate
methoxycyclobutane (88).
och3
(CO)5Re-H + (CO)NRe-
94
OCH3
Re2(CO)5+N +
104
(CO)5Re-H
24
och3
r4
oo
\
3
+

92
22
M
In an effort to determine which scheme is the more
nearly correct, several experiments were carried out.
They fell into two basic areas. The first of these
concerned deuterium incorporation during photolysis in
deuterated solvents. The second involved observation of
the changes induced in the photolysis by the presence of
added reagents.
The products of the photolyses in deuterated benzene
and especially deuterated toluene were analyzed carefully
by 1H NMR and GC-MS and there was no evidence for


52
deuterium incorporation. This was especially important
for the hydrogen on carbon 1 of methoxycyclobutane (88)
since it must come from some intermolecular source. It
would seem reasonable that if this were a radical
mechanism and it were carried out in deuteriotoluene,
there would be some incorporation of the deuterium into
the products. This speaks against the radical mechanism,
but is obviously only negative evidence.
The second area of investigation concerned the
effects of added phosphines on the photolysis. When one
equivalent of triethylphosphine is present during the
photolysis, two significant changes are observed. First,
one can actually observe the presence of a metallohydride
in the NMR spectrum. The hydride that is observed is
the one substituted by two phosphine ligands (105).
co
pei3
oc ReH
1Q
Second, the ratio of methoxycyclobutane (88) to 1-
methoxycyclobutene (89) is no longer roughly 1:1. In the
initial stages of the reaction there is as much as a 5


53
fold excess of 1-methoxycyclobutene (89) over
methoxycyclobutane (88) .
H
och3
££
1
och3
/
+
(PEt3)2(CO)3Re-H
sa
5
As the photolysis is continued, the amount of the
metallohydride (105) present decreases and the ratio of
methoxycyclobutane (88) to 1-methoxycyclobutene (89)
returns to nearly 1:1. Towards the end of the photolysis
trace amounts of hydride substituted with a single
phosphine are detected. The number of phosphine ligands
present on a metallohydride is easily determined due to
the fact that phosphorus has a spin of 1/2. The net
result is that the presence of one phosphorus on the
metallohydride splits the far upfield peak in the 1H NMR
spectrum (5 to 6 ppm upfield from TMS) from the hydride
into a doublet and the presence of two phosphorus ligands
splits the hydride signal into a triplet.


54
Replacing the triethylphosphine with triphenyl-
phosphine or trimethylphosphite results in significantly
different, although related, results. The
triphenylphosphine acted almost as if it weren't there.
Although detectable, the hydride never built up to a very
high concentration and the ratio between
methoxycyclobutane (88) and 1-methoxycyclobutene (89) was
unchanged as the reaction progressed. The presence of
trimethylphosphite resulted in a very rapid growth of the
peaks due to the hydride and then an equally rapid
decrease. This also left the ratio of methoxycyclobutane
(88) to 1-methoxycyclobutene (89) unchanged. A
reasonable explanation for this is that the
triphenylphosphine is not taken up during the reaction
and the trimethylphosphite is, but the hydride
substituted with two molecules of trimethylphosphite
reacts rapidly to generate the methoxycyclobutane and
metal dimer.
All of the mechanisms presented above can account for
these observations. In the beta hydride abstraction
mechanism a simple way to account for this is to have the
addition of one triethylphosphine be faster than the
rearrangement of the acyl complex (78) to the sigma
complex (79).


55
The second phosphine replaces the 1-methoxycyclobutene
(in 108) to form the diphosphine metallohydride (105)
which then slowly reduces the sigma complex (79) to give
the metal dimer (106) and methoxycyclobutane (88).
och3
v
PEi3(CO)3Re
H
PEt
3
(PEt3)2(CO)3Re-H
1Q5
och3
/
SS
108


56
Either radical mechanism can account for this simply by
having the rhenium pentacarbonyl radical (55) substitute
two phosphines, the second more rapidly than the first.
There is literature precedent for the rapid exchange of
phosphines on radical centers, with different phosphines
substituting at different rates and with differing
amounts of mono- and di-substitution.37
(CO)5Re 2PEt3 (PEi3)(CO)4Re (PEt3)2(CO)3Re
55 m Ufl
To distinguish between radical and non radical
mechanisms two samples of the 1-methoxycyclobutyl-l-
carbonylrheniumpentacarbonyl (78) were photolyzed in
benzene in the presence of triphenylmethane and p-methoxy
phenol, respectively. It was hoped that these compounds
would donate hydrogen atoms to any 1-methoxycyclobutyl
radicals (93)present, thus increasing the ratio of
methoxycyclobutane (88) to 1-methoxycyclobutene (89).
The triphenylmethane had no effect. The ratio remained
at roughly 1:1. In contrast, photolysis in the presence
of 5 fold excess of p-methoxy phenol resulted in a large
increase in the amount of methoxycyclobutane (88). The
final ratio was 4.3:1 in favor of methoxycyclobutane


57
(88). This is very strong evidence in favor of the
presence of the methoxycyclobutyl radical in the
solution, supporting the radical mechanism. There was no
reaction of the p-methoxyphenol with the acyl complex
(78) in the absence of photolysis. In addition, it will
be shown later that p-methoxyphenol does not react with a
complex that is very similar to sigma 79, the only
difference being that the cyclobutane ring is
benzannelated (i.e. complex 130). This indicates that p-
methoxyphenol is not a strong enough acid to form
methoxycyclobutane (88) in the absence of a radical
reaction.
Qualitatively the rate of the reaction was not
affected by the presence of p-methoxyphenol. If the
chain mechanism were operating, one would expect a
decrease in the rate of reaction.


58
This would come about as a result of the trapping of
the rhenium pentacarbonyl radical (55) to give the
hydride (94). Since the radical (55) is the chain
propagating agent, the chain would neccessarily be
broken. The lack of an observable rate decrease speaks
strongly against a chain mechanism.
It has been shown by Heinekey and Graham38 that 7-
carbonylcycloheptatrienerhenium pentacarbonyl (111) may
be decarbonylated to the corresponding sigma complex
(112) by photolysis in deuterated acetone at low
temperature.
We decided to follow his example and also expand on
it. We carried out photolyses of the methoxycyclobutyl
acyl complex (78) not only in deutero acetone at -65C,
but also at room temperature and in deuterated toluene at
-65C to try to synthesize the sigma complex (79) The


59
products were characterized by 1H NMR and also GC-MS. At
room temperature the organic products of the photolysis
in deuterated acetone were characteristic of a free
radical mechanism.
o
tight
(CD3)2CO
Room temp.
H
OCH3
S£
+
OH
ch3o
CCD3
I
cd3
ill
och3
/
+ MeOH
§9 62


60
Since this did not result in the desired product, we
cooled the sample to -65C during the photolysis of the
acyl complex (78) in deuterated acetone. This gave only
three organic products. These products were 1-
methoxycyclobutene (89), methoxycyclobutane (88), and 1-
methoxycyclobutanecarboxaldehyde (115) in a 1:0.56:0.40
ratio, again products typical of a free radical reaction
H
OCH3
M
0.56
och3
y
+
S2
1 0.40
The low temperature (-65C) photolysis was repeated
except in deuterated toluene* The products were the
same. The amount of methoxycyclobutane (88)could not be
determined due to overlap of its methoxy signal with
unreacted starting material (78) The ratio of aldehyde
(115) to alkene (89) was 0.5:1.


61
H
OCH3
SB
OCH3
/
89
1
A reasonable explanation for the observation of the
aldehyde (115) at low temperature is that at room
temperature after absorption of the first photon and loss
of CO the migration of the cyclobutyl group to the metal
center is relatively fast. By the time the photon comes
which converts the molecule to radicals, the molecule is
already a sigma complex (79). The radicals, hence, are
the rhenium pentacarbonyl radical (55) and the 1-
methoxycyclobutyl radical (93). At low temperature,
however, the migration is not nearly so fast. After the
ejection of the CO the methoxycyclobutyl group does not
migrate to the metal immediately. This allows time for
the ejected CO to return to the vacant site. The low
temperature would also aid this process due to the
decrease of rates of diffusion near the vacant site,
increasing the length of time the CO spends in the
vicinity of the metal and hence increasing the
probability of return. This decreases the efficiency of


62
the decarbonylation and increases the probability that a
relatively inefficient process that depends on the
concentration of the acyl complex (78) (i.e. homolysis to
generate radicals 116 and 55) will become significant.
(CO)5Re +
55
OCH3 0
S
m


63
In addition, the photolysis of the cyclobutyl acyl
(78) was performed under 6.3 atmospheres of CO at room
temperature in CgDg. There were no observed changes in
either the rate of reaction or the products (i.e.,
methoxycyclobutane (88) and 1-methoxycyclobutene (89))
compared to an identical sample photolyzed side-by-side
with the CO pressurized sample except under 1 atmosphere
of N2. This is consistent with the product forming
reaction being faster than the reaction of 106 with CO.
At this point we felt we had enough information to
make a reasonable postulate as to what was happening.
Upon photolysis the vast majority of the photons which
were absorbed resulted in the ejection of a molecule of
CO. At room temperature the cyclobutyl group migrated
rapidly to the metal center. At low temperature there
was only partial migration. The next productive reaction
was the homolysis of the Re-C bond through absorption of
another photon to generate the metal radical (55) and
either the methoxycyclobutyl radical (93) (at room
temperature) or the methoxycyclobutyl acyl radical (116)
(at low temperature). This brings up an interesting
point: why (at room temperature) is the first productive
reaction upon absorption of light the ejection of CO and
the second productive reaction upon absorption of light


64
the loss of the alkyl radical? It seems unlikely that
the electronic structure of the rhenium pentacarbonyl
moiety is so drastically different when it has an alkyl
ligand attached compared to when it has an acyl ligand
attached that there is no loss of CO in the alkyl case
and all photons cause homolysis to the radicals. The
upshot is that there is probably loss of CO from the
alkyl case, but it comes back in to the vacant site.
This is important since it points out that the cyclobutyl
ring did not rearrange to form a carbene even though
there was a vacant coordination site present to permit
it. This indicates that the rearrangement was either
endothermic or had a high energy of activation. We
decided to lower the energy of the desired carbene
complex. If the lack of rearrangement was due to the
rearrangement being endothermic, this change might induce
the formation of the desired carbene. If the problem lay
in the activation energy, this change might help also due
to the Hammond postulate.
Just as an electron-donating group on a carbene
carbon stabilizes the complex, it has been shown that
replacement of a CO on a metal complex by a phosphine
also stabilizes the complex.39 We decided to replace one
of the CO's on the cyclobutyl acyl complex (78) with a


65
triethylphosphine group and compare its (107) reactivity
with that of the analogous unsubstituted complex (78).
This substitution was accomplished by simply heating
the unsubstituted acyl (78) with 1 equivalent of
triethylphosphine in benzene for 6 hours at 70C.
The reactivity, unfortunately, was exactly the same
as before the substitution. Thermolysis resulted in a
very complex mixture of products. The 13C NMR spectrum
did not show the presence of the characteristic low field
peak indicative of a carbene carbon. The photolysis in
benzene produced a mixture of methoxycyclobutane (88) and
1-methoxycyclobutene (89) in a roughly 1:1 ratio.


66
The photolysis in deuterated acetone at -65C gave
1-methoxycyclobutene (89), methoxycyclobutane (88), and
1-methoxycyclobutanecarboxaldehyde (115) in a 1:0.42:0.47
ratio.
o
Light
(CD3)2CO
-65C
och3
och3
och3
6
1
H
££
£2
115
0.42
1.0
0.47
A mechanism which incorporates all of the data is as
follows:


67
och3
(CO)5Re
79
(CO)5Re
55
22
PEt3
Fast
(PEt3)2(CO)3Re
108
22
(PEt3)2(CO)3Re-H
+
m
£2
Re^CO^PEt^
m


o
68
(CO)sRe
55
OCH
/
3
22
OCH-,
(CO)sRe-H
2
£2
OCH,
22
OCH,
\!
Re2(CO)10
2
S£


69
och3
££
OCHj
(CO)5 Re +
55
+ (CO)5Re
5S
£9
+ (CO)5Re-H
24


70
(CO)5:
(CO)5Re
Re'
OCH,
OCH,
Light
Acetone-Dft
(CO)5Re -
-65 C
22
OCH,
(CO)5Re -
22
22
OCH-,
. (CO)5Re +
52
22
OCH,
22
OCH,
X
22
(CO)5Re-H
24
112
(CO)5Re +
25
112
22


71
The direct methods of forming a carbene complex from
a cyclobutyl complex were obviously not giving the
desired results. An indirect method was sought which
might allow a system to undergo a rearrangement of the
type under study. An effort was made to put the
possibility of beta hydride abstraction to our advantage.
It has been shown in the iron system that the trans beta
methoxy cyclobutyl sigma complex (120) will, upon loss of
CO, isomerize to the alpha methoxy sigma complex (99) and
then rearrange to the carbene complex (83).13
22
£2
It was hoped that the analogous rhenium pentacarbonyl
complex (121) would undergo similar rearrangements.


72
(CO)5Re
OCH3
121
(CO)4Re
122
OCH3
(CO)4Re
och3
H
2Q
och3
(CO)4Re
25
(CO)4Re
och3
m
There is one major advantage to using this indirect
pathway. It stems from the fact that we were unable to
isolate any alpha methoxy sigma complex (79) from the
previous work. This indicates that it (79) is either a
highly reactive species which decompose to something
other than the desired carbene complexes or was never
formed. The mechanistic results detailed previously
(e.g. the formation at room temperature of
methoxycyclobutane (88) and 1-methoxycyclobutene (89) but
no 1-methoxycyclobutanecarboxaldehyde (115)) argue that
the sigma complex (79) is formed. If sigma complex 79 is
formed it decomposes to compounds other than the desired
carbene comlex (80). The advantage of the above scheme
is that once the alpha methoxy sigma complex (95) is
formed in the indirect pathway there is already a vacant


73
coordination site on the rhenium. It was hoped that this
would increase the probability of the rearrangement to a
carbene (80) happening as opposed to decomposition
pathways.
The synthetic strategy involved the reaction of
cyclobutene epoxide (123) with rhenium pentacarbonyl
anion (35) followed by trapping by CH3I.
(CO),Re- +
21
m
(CO)5Re
124
CH3I
(CO)5Re
OCH3
121
The cyclobutene epoxide (123) was synthesized by
literature methods. The first step involved the
reduction of commercially available cyclopropane
carboxylic acid (125) with LiAlH4 to the alcohol (126).40
LiAlH,
ch2oh
121
The second step was isomerization of the cyclopropyl
carbinol (126) to cyclobutanol (127) via acid
catalysis.^9 This compound (127) was then converted to


the tosylate (128) by reaction with tosyl chloride in
pyridine.39
H+
OH
TsG
h2o
Pyndine
127
128
OTs
The tosylate (128) was then treated with potassium
t-butoxide in DMSO to form cyclobutene (129). The
cyclobutene (129) was collected and bubbled through
a -20C solution of m-chloroperoxybenzoic acid in CH2Cl2.
This mixture was then stirred for 3 days at 0C. The
solvent was carefully removed by Vigreaux distillation.
The final purification of the cyclobutene epoxide (123)
was accomplished by preparative gas chromatography.^1
o
OTs
KOlBu
[=1
mCPBA /_\
DMSO
' 1 1
CH2C12 1
128
-20C
122
The results of the addition of rhenium pentacarbonyl
anion (35) to the cyclobutene epoxide (123) followed by
trapping with methyl iodide were very disappointing. The
only isolated organometalic product was (CO)5Re-CH3, and


75
this was only in trace amounts. Apparently the
nucleophilicity of the rhenium pentacarbonyl anion (35)
is not sufficient to open up the epoxide (123). The
anion (35) simply does not react and slowly decomposes.
The small amount that remained eventually attacked the
methyl iodide.
A short summary of the major points of this project
is in order. The first attempt involved the use of 1-
alkoxy substituted cyclopropane (44) to achieve the
desired rearrangement. The requisite sigma complex (45)
could not be formed from the acyl complex (44). The 1-
ethoxycyclopropyl sigma complex (66) could not be formed
either via nucleophilic attack on a rhenium halide (39,
76) or from nucleophilic attack of a rhenium
pentacarbonyl anion (35) on 1-bromo-l-ethoxycyclopropane
(65) .
The decarbonylation of the 1-methoxycyclopropyl acyl
complex (44) resulted in homolytic cleavage of the Re-C
bond. This was attributed to the reluctance of the
cyclopropane to migrate to vacant coordination sites on
the metal.


76
The attempt to solve the problem of the lack of
migration from acyl to alkyl by going to the 4 membered
ring seems to have been successful.
This brought with it a different problem. The metal
seemed to be removing a beta hydrogen from the sigma
complex (79) during radical decomposition.
Before we had conclusively found that the mechanism
of decomposition was via radicals, we searched for a
system which would be immune to the problems encountered
previously. It must not involve a cyclopropane, it must
have a methoxy in the alpha position, and either have no
beta hydrogens or beta hydrogens which, if they


77
rearrange, would give a pi complex that would not
dissociate.
The system which was chosen satisfied all of these
requirements. This system was the 7-methoxy-7-
rheniumpentacarbonyl-benzocyclobutene system (130).
(CO)sRe
OCH3
There is obviously no cyclopropane. Molecular mechanics
calculations42 indicate that opening the 7-methoxy-
benzocyclobutene system can relieve more strain (48.5
kcal/mol) than the opening of either the methoxy-
cyclopropane (28.1 kcal/mol) or methoxycyclobutane (26.1
kcal/mol) systems. The problem of beta hydrogens is
solved elegantly. The solution to the problem lies in
the fact that if a beta hydrogen should be removed then
the product would be a methoxycyclobutadiene derivative.
If the hydrogen were removed via a beta hydrogen
abstraction then the methoxycyclobutadiene would be
complexed to rhenium (131).


78
Although cyclobutadiene complexes are known,the
cyclobutadiene moiety is complexed tightly to the metal.
We expected that the hydride ligand on the same metal
would react with the cyclobutadiene ligand to regenerate
a sigma complex (130) which would then rearrange to a
carbene complex. This would be completely analogous to
the iron pi complex (100) to sigma complex (99) to
carbene (83) series of rearrangements shown earlier.13
If the beta hydrogen were removed by a radical
process, then, assuming the same reactivity as in the
non-benzannelated case, the cyclobutadiene would be the
free molecule (132).


79
(CO)jRe
55
(CO)5Re
OCH3
to
(CO)5Re-H £4
(CO)5Re 15
We would not expect either of these processes to take
place due to the large amount of ring strain that would
be introduced due to the formation of the cyclobutadiene
ring. Molecular mechanics calculations42 were used to
quantify this. They indicated that converting
methoxycyclobutane (strain = 26.1 kcal/mol) to 1-
methoxycyclobutene (strain = 33.0 kcal/mol) involves an
increase of 5.9 kcal/mol in strain energy. They also
indicated that converting 7-methoxybenzocyclobutene
(strain = 48.5 kcal/mol) to 7-methoxybenzocyclobutadiene


80
(strain = 66.0 kcal/mol) involves a 17.5 kcal/mol
increase in strain energy.
Unfortunately the synthesis of the target molecule
(130) was very difficult. There were two major pathways
which were undertaken. The first involved pre-forming
the entire methoxybenzocyclobutene fragment (133) before
attaching it to the metal center.
och3
(CO)5Re
The second pathway involved forming the benzocyclobutene
fragment (134), attaching it to the metal, then putting
the methoxy group in place.


81
9ch3
(CO)5Re
130
The former procedure was attempted first for two reasons.
The first is once a metal is involved in a reaction our
experience has shown that a wide variety of unexpected
reactions may take place. The former sequence involves
fewer steps once the metal is attached. The second
reason is that the cationic rhenium pentacarbonyl carbene
complex (137), which is critical to the sequence, is
unknown. More broadly, there are no references in the


82
literature to any cationic rhenium pentacarbonyl carbene
complexes. The analogous dicarbonyl(n5-
cyclopentadienyl)iron compound (138) has been known for
some time, however.44
The overall synthetic sequence that was begun for the
former plan is as follows:
:CBr2
Br -CN
iYY
140
Hi
139


83
OH
h2o
r cojH
M2
l~i Base
2) 02
3) H20
OH
COjH
The steps up through the carboxylic acid (142) are all
known from the literature. The bromobenzocyclobutene
(140) was synthesized by heating cycloheptatriene (139)
and bromoform in the presence of a base (K2CO3) and a
catalyst (18-crown-6).45


84
CHBr3 + K2C03
18-C-6
140
f^T
140
This bromide (140) was then treated with KCN in DMSO
to replace the bromine with a nitrile (141).46 Finally,
the nitrile was hydrolyzed to the acid (142) by treatment
with KOH/EtOH/H20.47
141
KOH
EtOH
HiO
79C
CO2H
142
The sequence from cycloheptatriene (139) to the acid
(142) was very interesting from a pragmatic point of
view. As one might expect, the first step was a very
messy reaction. There are several impurities in the same
fraction of the distillate as the bromobenzocyclobutene
(140). After repeated attempts we were able to re
distill the mixture and obtain pure product (140).
Unfortunately a great deal of the product was lost during


85
the purification. In order to avoid this loss, we tried
to carry the impurities along to the nitrile stage (141)
and separate them then. This was unsuccessful. The best
method by far was to carry the impurities all the way
through to the acid stage (142). All of the impurities
are considerably more volatile than the acid (142).
Simply applying a vacuum (0.01 torr, 25C) removes all of
them, leaving the acid as a white solid.
The rest of the planned synthetic sequence was
completely analogous to that of the non-benzannelated
system (87). The introduction of the methoxy group would
be accomplished by treatment of the acid with two
equivalents of strong base followed by oxygen and work-up
to give the alcohol which could be methylated by
treatment with base and CH3I.
The introduction of the alcohol to give 143, gave an
inseparable, complex mixture. After several attempts at
direct purification we decided to carry all the compounds
through to the methoxy stage (144) and purify the mixture
then. The crude mixture was treated with NaH/Cl^I to
convert the alcohol into a methoxy group. This gave a
product mixture that was partially resolved by column
chromatography. It gave 4 mixtures of 2 major components
each. Examination by FT-IR and 13C APT spectroscopy


86
revealed that none of the 8 compounds could be the
desired alpha methoxy benzocyclobutene carboxylic acid
(144) .
At this point we reexamined the second strategy.
This involved making the benzocyclobutene acyl complex
(135), decarbonylating it to the alkyl complex (136),
converting it to the benzocyclobutenylidene carbene
complex (137), and then adding methoxide to give the
alpha methoxybenzocyclobutene sigma complex (130).
o
(CO)sRe-
136
Ph,c*Bry
BF,
(CO)sRe^
137
There are two obvious problems associated with this
strategy. The first is that it requires a successful
decarbonylation from an acyl complex (135) to a sigma
complex (136) and in our hands none of our attempts had
been successful on rhenium pentacarbonyl systems. The


87
second is the intermediacy of the benzocyclobutenylidene
carbene complex (137) as mentioned above. Not only is
this not a known compound, there are to my knowledge no
known cationic rhenium pentacarbonyl carbenes. A
previous attempt to form methylidene rhenium
pentacarbonyl cationic complex was unsuccessful.48
(CO)5Re-CH3
Ph3C*BF4-
(CO)5Re-F-BF3
Finally the sequence requires that not only must the
benzocyclobutenylidene complex (137) be synthesized and
be at least moderately stable, but it must react with
methoxide to give the addition product (130).
Taking this into account we started the sequence.
The benzocyclobutene carboxylic acid (142) was treated
with oxalyl chloride to generate the corresponding acid
chloride (143). This went smoothly. Treatment of the
acid chloride (143) with rhenium pentacarbonyl anion (35)
(generated as before) gave the desired acyl (135) in a
clean reaction.


88
142
134
O
iCO)5Re
(CO)5Re
\ H
(CO)5Re
35
135
The acyl complex (135) was dissolved in toluene-Dg and
heated to 105C. The thermolysis was monitored by 1H
spectroscopy. This showed that the decarbonylation went
smoothly and was complete in 90 minutes. The sigma
complex (136) decomposes only very slowly at this
temperature. This degradation is indicated by a slow
growth of peaks in the vinylic region of the 1H NMR
spectrum.
o
135


89
The next steps were more difficult. Addition of
trityl tetrafluoroborate to a methylene chloride solution
of the sigma complex (136) produces a deep red color.
This color gradually changed until after approximately
one hour the solution had become dark green. If one
follows this reaction by looking at the absorptions of
the terminal carbonyls in the IR spectrum of the mixture,
one sees a shift to higher wavenumbers after 15 minutes.
This is then followed by a change in the relative
intensities of these peaks, but no general, overall
shift. The addition of methoxide/methanol to this dark
red solution immediately changes the color to light
yellow.
Column chromatography revealed 4 types of compounds.
The first to be eluted was triphenylmethane (146). This
comes from the abstraction of a hydride by the trityl.
The yield of this is very high (e.g. 91%).
136


XTRANSUITUNCE
15 087 27 066 59 049 51 030
cr*
R1 DfNZO 5IGUA BTFORF ADDING IRII.I (III2U2)
u
to
1 ffl
1 ?
hl
r
1
Y -
bO
7 1 6

I :
l
Y *
Y-
1b 1
804
2 127
3
Y 3
67
l 1 0
2
56
6
Y -
7 1
090
2
06
2
Y -
2 1
084
2
1 1
3
Y -
5 1
396
2
73
6
Y =*
74
440
2-
7 7
7
Y
74
453
2
79
9
Y -
74
5 36

li
1
5
T -
r =
6 4
73
056
150
2566
25 7 2
6
3
Y -
74
74
1 1 0
I 08
U i
n l niQ
Delei
1 e d
7i>35 3 2365 0 2 197 3 2 112 I 202 7 0 19 4 1 8 1856 6 17 7 1 4 lb8b 3 IbOl I
WWCNUUBERS (C-1)
Figure 9
IR of Benzocyclobutene-7-rhenium-
pentacarbonyl(136)


ztramsuittancc
19 324 29 139 39 953 50.2(7 (0 552 70 896
O
RE BNZO SIGUA AF1ER ADO I R 1 I FL vA/ANU l RI (IHZU)
Figure 10: Reaction of Benzocyclobutene-7-rhenium-
pentacarbonyl with triphenylcarbenium
tetrafluoroborate


92
The second compound to elute is trityl methyl ether
(147). This comes from the reaction of unreacted trityl
tetrafluoroborate with methanol.
Ph3C* bf4
MeOH
PhjC-OMe + HBF4
142
The third is the desired sigma complex of alpha
methoxybenzocyclobutene (130). This comes from the
reaction of the benzocyclobutenylidene carbene (137) with
either methanol (followed by deprotonation by methoxide)
or methoxide.
+
148
122
OMe
OCHa
130


Full Text

SCOPE AND LIMITATIONS OF THE 1,2 REARRANGEMENT
OF ALKYL GROUPS FROM CARBON TO METALS
TO GENERATE CARBENE COMPLEXES
By
PAUL K. HANNA
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
1988
[U OE F libraries

ACKNOWLEDGEMENTS
I would like to thank William M. Jones for his
patience and help throughout the years.
I would like to thank the people in the lab for their
help and encouragement, especially Yngve Stenstrom,
Su-Min Oon, Wayne Chandler, Nick Conti, Donna Crowther,
Rhonda Trace, Jasson Patton and Laura Quinn.
I would like to thank those people outside the lab
for reminding me (often!) that there is always a light at
the end of the tunnel. There are too many of these
people to mention, but Ted Streleski is not the least of
them.
Finally, a very special thanks to Jeanne Pittari,
Paul Hanna, and Mary Hanna; I couldn't have done it
without them.
11

TABLE OF CONTENTS
ACKNOWLEDGEMENTS ii
ABSTRACT vi
CHAPTERS
1 INTRODUCTION 1
2 RHENIUM 9
3 IRON 104
4 CONCLUSION 129
5 EXPERIMENTAL 132
General Procedures 132
Preparation of 1-Methoxy-l-
thiophenylcyclopropane (51) 133
Preparation of 1-Methoxycyclopropane-
carboxylic acid(53) 134
Preparation of 1-Methoxycyclopropane-
carbonylchloride (47) 135
Preparation of Pentacarbonyl(1-methoxy-
cyclopropyl-1-carbonyl)rhenium(44) 136
Photolysis of Pentacarbonyl(1-methoxy-
cyclopropyl-l-carbonyl) rhenium (44) 137
iii

Preparation of 1-Bromo-l-ethoxy-
cyclopropane(65) 139
Preparation of 1-Ethoxy-l-trimethyl-
siloxycyclopropane(70) 140
Preparation of Bromotetracarbonyl-
(triphenylphosphine)rhenium(75) 141
Preparation of Methyltetracarbonyl-
(triphenylphosphine)rhenium(76) 142
Preparation of (1-Ethoxycyclopropyl)-
phenylmethanol(77) 143
Preparation of 1-Methoxycyclobutane-
carboxylic acid(86) 144
Preparation of Pentacarbony1(1-methoxy-
cyclobutyl-1-carbonyl)rhenium(78) 146
Photolysis of Pentacarbonyl(1-methoxy-
cyclobutyl-l-carbonyl)rhenium(78) 147
Preparation of cis-Triethylphosphine-
tetracarbonyl-l-carbonyl(1-methoxy-
cyclobutyl) rhenium (107) 150
Photolysis of cis-Triethylphosphine-
tetracarbonyl-l-carbonyl(1-methoxy-
cyclobutyl) rhenium (107) 151
Preparation of Cyclopropylcarbinol(126) 153
Preparation of Cyclobutanol(127) 154
Preparation of Cyclobutyl Tosylate(128) 155
Preparation of Cyclobutene Epoxide(123) 156
Preparation of 7-Bromobenzo-
cyclobutene (140) 158
Preparation of 7-Cyanobenzo-
cyclobutene (141) 159
Preparation of Benzocyclobutene-7-
carboxylic Acid(142) 160
IV

Preparation of Benzocyclobutene-7-
carbonyl chloride (14 3) 161
Preparation of Benzocyclobutene-7-
carbonylrheniumpentacarbonyl (135) 161
Preparation of benzocyclobutene-7-
rheniumpentacarbonyl(136) 163
Preparation of Benzocyclobutene-7-
methoxy-7-rheniumpentacarbonyl(130) 164
Thermolysis of Benzocyclobutene-7-
methoxy-7-rheniumpentacarbonyl (130) 166
Preparation of Dicarbonyl-(n5-cyclopenta-
dienyl) (propyl) iron (162) 167
Preparation of Dicarbonyl-(n^-cyclopenta-
dienyl)- 2-propenyliron tetra-
fluoroborate (163) 168
Preparation of Dicarbonyl(n5-cyclopenta-
dienyl)[2-(N,N-dimethylamino)prop
-1-yl ] iron (165) 169
Photolysis of Dicarbonyl(n5-cyclopenta-
dienyl)[2-(N,N-dimethylamino)prop-1-
yl]iron(165). Isolation and Character¬
ization of Carbene Complex 169 and Chelate
Complexes 170 171
REFERENCES 17 5
BIOGRAPHICAL SKETCH 179
V

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
SCOPE AND LIMITATIONS OF THE 1,2 REARRANGEMENT
OF ALKYL GROUPS FROM CARBON TO METALS
TO GENERATE CARBENE COMPLEXES
By
Paul K. Hanna
December 1988
Chairman: William M. Jones
Major Department: Chemistry
This research investigates the generality of the
rearrangement of alkyl groups from carbon to metal. This
rearrangement had previously been observed only when the
metal was iron and the alkyl group was part of a strained
ring. In this research, systems were synthesized which
contained rhenium instead of iron and an acyclic alkyl
group instead of a strained ring.
The first system synthesized was pentacarbonyl(1-
methoxycyclopropyl-l-carbonyl)rhenium (44). Thermolysis
of this compound in toluene resulted in a complex mixture
which did not contain the desired rearranged product.
Photolysis of 44 in benzene resulted in formation of
vi

Re2(CO)10 and the dimer of the organic acyl fragment,
compound 54. The analogous pentacarbonyl(1-methoxy-
cyclobutyl-l-carbonyl)rhenium (78) was synthesized.
Thermolysis in toluene resulted in a complex mixture
which did not contain the desired rearranged product.
The photolysis of 78 was studied mechanistically. It was
shown to be a radical reaction involving metal hydrides
which generates
methoxycyclobutane (88)
and
1-
methoxycyclobutene
(89)
in a 1:1 ratio
at
room
temperature in benzene.
Photolysis at -65°C
forms 1-
methoxycyclobutanecarboxaldehyde (115) in addition.
The pentacarbonyl(7-methoxybenzocyclobutene)rhenium
system (130) was synthesized through the intermediacy of
pentacarbonyl(7-benzocyclobutenylidene)rhenium tetra-
fluoroborate (137). This is the first known cationic
rhenium pentacarbonyl carbene complex. Thermolysis of
130 resulted in formation of benzocyclobutenone and
pentacarbonyl(7-benzocyclobutene)rhenium (136) with an
activation energy of 21.1 kcal/mol and an entropy of
activation of -2.1 cal/mol-K. The acyclic iron system
dicarbonyl- (n5-cyclopent adienyl) [2 - (N, N-dimethylamino) -
prop-l-yl]iron (165) was synthesized and photolyzed. The
desired rearranged product (169) was isolated as
indicated by spectroscopy and chemical reactivity.
vii

CHAPTER 1
INTRODUCTION
The area of research into the chemistry of
organotransition metal carbene complexes was given a
boost when C. P. Casey and T. J. Burkhardt showed for the
first time in 1974 that such a compound (1) could induce
metathesis.1 This was significant in that it allowed the
interconversion of alkenes. One could start with
relatively simple alkenes and transform them into more
complex ones in a single step.
CeHs
(CO)s
c6h5
1
The splitting up of alkenes and their recombination is
both interesting from a mechanistic point of view and
practical in that a variety of alkenes may be synthesized
easily such as 1,1 diphenylethylene (4) in the example
above.
During the course of a theoretical study on these
carbene complexes H. Berke and R. Hoffmann2 investigated
the 1,2 migration of a carbon from a carbon to a metal
1

2
resulting in the formation of a carbene complex. The
reaction they specifically studied was the manganese
tetracarbonyl ethyl complex (5) rearranging to the methyl
manganese tetracarbonyl methylidene complex (6). The
calculations predicted that the energy of activation
should be essentially the same as the energy difference
between the two molecules. This indicates that the
activation energy for the rearrangement is nearly zero.
co
oc M rv-— CH2-CH3
/I
oc' CO
ch3 CO
1/
oc— M n = CH2
/I
oc' CO
5
6
In contrast to this predicted facile rearrangement
there was until recently only one reported case in which
there was any evidence that an alkyl group migrated from
a carbon to a metal to generate a carbene complex.3 This
was a case in which the metal was Ni and the presumed
carbene complex (8) was unstable, its existence was
inferred from the resulting chemistry which involved the
trapping of the intermediate carbene (8) with cyclohexene
to generate the norcarane (9).

3
There are a great many processes which involve an
analogous rearrangement, the migration of hydrogen to the
metal center instead of carbon.4'5'6
Cpj
10
-c2h4
cd3
+ /
Cp2W
11
D
+ /
Cp2W
12 'CD2
PMe2Ph
PMe2Ph
PMe2Ph
D
Cp2W
Cp2W,
cd3
\
11
14
CD2-PMe2Ph
D-.
(PPh3)3M -CH3 CD4 + CD3H + CD2H2 + CDHj + CH4
15
M = Co, Rh
There are, however, many cases known in which an
alkyl group on a metal center migrates to a carbenic

4
carbon which is on the same metal. This results in the
destruction of the carbene center and the formation of a
new C-C bond.7'8'9
â– +/
Cp.w
\
ch3
C6H5
-H
CHjCN
CpjW
/
ch2
c6h5
17
ch2c6h5
CV2v/
13.
CHjCN
+ CH2C6H5
Cpjv/
NCCH3
15
I 3 PMe3
+ I /
Br — I r CH2
Me3P^ I
PMe3
PMe3
+ /
Br—I f- CH2-CH3
Me3p/F>Me3
20
21

5
ch3
ch2-ch3
Cp2vf
22 CH3
-H
♦/
Cp2W
23 CH3
24
+
A
Cp2\V
\
H
25
All of these facts point to the conclusion that the
predicted facile equilibrium of Berke and Hoffmann2 is
not an equilibrium at all for carbon systems. The
rearrangement normally goes in the direction that leads
to the destruction of the carbene center. The reason for
this "one way equilibrium" has been postulated by N. J.
Cooper and M. L. H. Greene to be one of thermodynamics.3
In an organometallic system in which there is a vacant
coordination site on the metal such a migration is often
possible. When the migration of an alkyl group from a
carbon to a metal center occurs the net result is the
loss of a C-C bond, the formation of a M-C bond, and the
conversion of a M-C bond into a M=C bond. This change
was thought to be thermodynamically unfavorable. The
molecule would invariably find some other, more
energetically favorable, pathway to fill the vacant
coordination site. It is important to note that if this

6
theory is correct, the rearrangement of an alkyl group
from a carbon to a metal generating a carbene complex may
be brought about if the system is perturbed so that the
rearrangement is energetically favorable.
Chemists have long known that the way to shift the
position of an equilibrium is to change the thermodynamic
preference on one side relative to the other. One way to
do this is to decrease the energy of the less favored
side. The other is to increase the energy of the more
favored side.
Energy
While working towards a completely different goal,
Jim Lisko serendipitously employed both of these
techniques and discovered that the rearrangement of alkyl
groups from carbon to metal centers could not only be
made to occur, but to give a stable carbene complex
containing an organic ligand bonded to the metal
center.^

7
The organic ligand in the starting material contained a
cyclopropane ring (27), which expanded to a 5 membered
ring in the product (28). The ring strain of the
cyclopropane in effect raised the energy of the starting
material (27). A 5 membered ring,as is in the product
(28), is relatively unstrained and does not affect the
relative energies.11 The product (28) contained an
electron donating methoxy group on the carbene carbon.
These are known to stabilize12 carbene complexes of iron.
This, in effect, lowered the energy of the product. The
result of combining these two factors was that the
rearrangement occurred readily. This supported the
previous hypothesis of Cooper and Greene3 that
rearrangement normally does not occur because of
unfavorable thermodynamics.

8
A number of researchers undertook investigations to
delineate the scope of this rearrangement. The initial
efforts focused on a narrow area. The rearrangement was
only studied in systems containing iron bound to highly
strained rings with strongly electron donating groups in
the alpha position (29) and under photolytic
conditions.
N = 2.3
X = OR. NR,
The work that will be described here will be
investigations intended to generalize this rearrangement.
It will concern the efforts to initiate such a
rearrangement on a different metal center (which could
undergo the rearrangement thermally) and in an iron based
system in which the rearrangement might occur with no
ring strain in the starting material.

CHAPTER 2
RHENIUM
In an effort to extend this rearrangement to a
different metal system a thorough literature search was
undertaken. There were obviously a great number of
possibilities from which to choose a reasonable
combination of metal and ligands. This search resulted
in the choosing of the rhenium pentacarbonyl group as a
very promising metal system for this rearrangement.
There were a number of factors which helped in this
decision. The first was that rhenium is a third row
transition element. Third row transition elements are
known to form relatively strong single and double bonds
to carbon.12'14 This is generally attributed to their
larger d orbitals, the energies of which allow better
overlap with the carbon orbitals than the first row
elements are capable of. This increases the stability of
the resulting complexes. Indeed there are a wide variety
of stable rhenium acyl complexes (e.g. 31), alkyl
complexes (e.g. 32), and finally there are also carbene
complexes (e.g. 33).15'16'17
9

10
o
(COLRe
22
och3
(CO)4Re=^
ch3
Re(CO)5
22
It was believed that the existence of these closely
analogous complexes would presage the stability of the
complexes that this project would entail making.
The second factor that pointed to this system as the
system of choice was the fact that the rhenium
pentacarbonyl anion (35) is moderately nucleophilic.18
Relative
Nucleophilicity
Cp(CO)2Fe“
+
R-X
PhS“
+
R-X
(CO)5Re"
+
R-X
Cp(CO)3W"
+
R-X
(CO)5Mn“
+
R-X
R = CH3I, C2H5I, C2H5Br,
Cp(CO)2 Fe-R
7xl07
PhS-R
2.6x10
(CO)5Re-R
2.5x10
Cp(CO)3w-r
5xl02
(CO)5Mn-R
7.7x10
(CH3)2CHBr

11
It was presumed that this would be advantageous during
the synthesis of starting materials. One possible
synthetic strategy would be to first make the appropriate
organic substrate, then attach the metallic fragment via
a nucleophilic substitution reaction.
The third factor was the ease of synthesis of the
rhenium-containing precursors of the desired
organometallic compounds. The rhenium pentacarbonyl
anion (35), for example, is synthesized by a simple
sodium amalgam reduction of commercially available
dirhenium decacarbonyl (34).^9
Re2(CO)10
34
Na/Hg
THF
+
2 Na Re(CO)s
21
This could then serve as a nucleophile for reaction with
an organic moiety containing a strained ring (36) that
would generate the organometallic complex 37. This would
later undergo the ring expanding rearrangement to
generate a carbene complex.

12
If one treats dirhenium decacarbonyl (34) with
iodine, one can easily obtain (CO)5ReI (39).20
CHC1,
Re;(CO)]0 + h —-r 2(CO)5Re-I
M 22
In the reverse of the step mentioned above which
generated an organometallic complex (37) via nucleophilic
attack of the rhenium pentacarbonyl anion (35) on an
alkyl halide (36), this metal halide (39) could then be
attacked by an organic nucleophile (40) which contained
the strained ring, resulting in the generation of the
same sigma complex (37).
OCH,

13
Both of these methodologies arrive at the same types of
desired products, but from completely different
directions. Thus the choice of the rhenium pentacarbonyl
system provided a back up system for the formation of the
desired organometallic target compounds should our first
attempt fail.
The final factor which was in favor of the rhenium
pentacarbonyl system was the fact that the terminal
carbonyls are thermally labile. This is best exemplified
by the fact that one of the standard methods for forming
rhenium pentacarbonyl sigma complexes (e.g. 42) is
thermolysis of the corresponding acyl compounds (e.g.
(CO)5Re-CH3
42
The generally accepted mechanism for this transformation
involves initial dissociation of a terminal carbonyl
followed by migration of the alkyl group to the vacant
site on the metal center. The net result is the
conversion of an acyl complex (e.g. 41) into an alkyl

14
complex (e.g. 42) with the loss of one of the terminal
carbonyls.22
(CO)5Re-CH3
42
This is significant in that it provides a
thermal route to a vacant site on the metal center. In
the metal systems which were known to undergo the desired
rearrangement (e.g. the rearrangement of 29 to 30)
photolysis of the starting material was neccessary to
expel a CO and provide a vacant site for the
rearrangement. The thermal lability of the COs on the
rhenium pentacarbonyl system opens the possibility of
thermally initiating the desired rearrangement.
Whenever one is expanding one's area of knowledge,
the most rational approach in order to prevent utter
confusion is to change only one variable at a time and
see what effect it has. If this guideline is applied to
the attempt to search for a different metal system to
undergo the rearrangement, then it is obvious that the
organic fragment should be the same as one that is known

15
to rearrange in the original iron system. For this
reason it was decided to make pentacarbonyl(1-methoxy-
cyclopropyl)carbonylrhenium (44).
o
44
It was believed that this (44) could be either
thermolyzed or photolyzed to generate the sigma complex
(45). Upon further irradiation or heating this (45)
would undergo the desired rearrangement yielding the
carbene complex (46).
o
The synthesis of the starting acyl complex (44) was
accomplished without much difficulty. The basic plan was
to react the metal anion (35) with 1-methoxycyclopropane
carboxylic acid chloride (47).

16
This is the same pathway that was followed in the
original iron system (26). The (COJgRe- (35) was
synthesized easily in the fashion mentioned previously.
The synthesis of the acid chloride (47) was successful
although fairly time consuming. The starting material
was thiophenylcyclopropane (48), which was treated with
n-butyllithium to form the anion (49) and then I2 to form
the iodide (50).23
sc6h5
H
nBuLi
SC6H5
[X
sc6h5
X,
42
5Q
Treatment of this compound (50) with base (K2CO3) and
CH3OH converted the iodo substituted cyclopropane (50)
into a methoxy substituted compound (51).
t><
sc6h5
5Q
k;co3
SC6Hs
och3
¿1
MeOH

17
The next step was the conversion of the thiophenyl group
into a carboxylic acid. This was accomplished by
reductive cleavage of the thiophenyl group of (51) with
lithium naphthalenide and then bubbling C02 into the
reaction mixture.23'24 The methoxycyclopropyl anion (52)
attacks the C02 to generate 1-methoxycyclopropane
carboxylic acid (53). The yields are generally low and
highly variable. The byproducts (thiophenol and
napthalene) have a wretched stench.
sc6h6
IX
och3
1L
Li Nap
l)C02
co2h
[X
och3
THF
^OCH,
a
2) H3cr
When the product
(53) was obtained, however,
conversion
into the desired acid chloride (47) was easily effected
by treatment with oxalyl chloride. Purification was
accomplished by Kugelrohr distillation.

18
Finally, reaction of this acid chloride (47) with the
rhenium pentacarbonyl anion (35) gave the desired acyl
complex (44) in moderate yields (generally 40% - 50%).
o o
The next step was the decarbonylation of the acyl complex
(44) to form the alkyl complex (45).
This was expected to be a simple step, but it turned out
to be the one that brought this pathway to a complete
stop. We were unable to generate the 1-
methoxycyclopropyl sigma complex (45) from the acyl

parts per million
Figure 1: -*-H NMR of Pentacarbony 1 (1-methoxycyclopropyl-
l-carbonyl)rhenium(44)

parta par million
Figure 2: 13C NMR of Pentacarbonyl(1-methoxycyclopropyl-
1-carbonyl)rhenium(44)

o
Figure 3: IR of Pentacarbonyl(1-methoxycyclopropyl-l-
carbonyl)rhenium(44)

22
complex (44) synthesized above. Thermolysis in toluene
resulted in gross decomposition. There were a great many
products as shown by thin layer chromatography. All of
these products were in low yield and none could be
characterized adequately. We next turned our attention
to the photochemical decarbonylation of this acyl complex
(44). The photolysis in deuterobenzene was a very clean
reaction. There were only two products. These were
shown to be the dimers of the metallic fragment (34) and
the organic fragment (54).
The inorganic dimer (34) was characterized by TLC and
FTIR. The organic dimer (54) was characterized by ^-H
NMR, FTIR, and GC/MS.
These results indicate that the main productive
process is homolysis of the Re-C acyl bond in (44) and
subsequent dimerization of the radicals (55 and 56).

Figure 4: Photolysis of Pentacarbony1(1-methoxy-
cyclopropyl-1-carbonyl)rhenium(44)

o
o
Examination of this failure to decarbonylate shows
that it is not without precedent.15 There have been
references in the literature to other cyclopropyl acyl
complexes (57) that could not be decarbonylated to the
corresponding alkyl complexes.
M = CpFe(CO)2
(CO)5Re
(CO)5Mn

25
It is generally acknowledged25 that in photochemical
decarbonylations there are two competing processes: the
first is homolysis of the M - C bond; the second is the
photoexcitation and subsequent dissociation of CO from
the metal center. It seems reasonable, therefore, that
if for some reason the migration of our
methoxycyclopropyl group to the metal were proceeding
either slowly or not at all, then the vacant site on the
metal center would have time to pick up a CO from
solution. This would regenerate the starting material
(44) and make the dissociation a non-productive process.
The homolysis to form the radicals 55 and 56 would be the
only observed process.
Further examination of the literature reveals that
the migration of a recalcitrant cyclopropane from an acyl
carbon to a metal center is highly solvent dependant. In
the iron case mentioned above the reaction was later
shown to go cleanly in acetone but only very poorly in
petroleum ether.26

26
The photolysis of the rhenium methoxycyclopropyl acyl
complex (44) was consequently tried in acetone. The
results were significantly different. The most obvious
result was that there were a large number of products.
Analysis of the volatiles by capillary gas chromatography
revealed 15 components. Product identification was
attempted by GC/MS. Unfortunately the poorer quality of
the separation on this instrument resulted in the
identification of only 5 of these components: 54, 60, 61,
62, and 63.

27
MeOH
61
The problem seemed to be that we were unable to form
the needed sigma complex (45) that could undergo the
rearrangement. The presence of the carbonyl-containing
compounds (54, 60, and 61) indicates that cleavage is
taking place before the alkyl group shifts to the metal
center. The presence of methoxycyclopropane (62) may be
explained in two ways. The first is that the sigma
complex (45) was formed and then decomposed via radicals

28
55 and 64. The second is that the acyl complex (44)
decomposed to an acyl radical (56) which then lost CO to
generate the methoxycyclopropyl radical (64) and then
picked up the H. We have no evidence to favor either of
these mechanisms.
-CO
(CO)., Re
OCH3
/
(CO)5Re
55
O
ch3o
56
-CO
(CO)5Re
55
XJ
ch3o
£4
Since we were unable to obtain the desired sigma
complex through decarbonylation, we decided to attempt to
avoid the intermediacy of the acyl complex (44) and
synthesize the sigma complex (45) directly. There were
two ways we could go about this. We could either use the
rhenium pentacarbonyl anion (35) as a nucleophile and

29
attack an appropriately substituted alkoxycyclopropane
(36 or 65) in the alpha position or we could use a
nucleophilic alkoxycyclopropyl anion (40 or 67) and
displace a leaving group from the rhenium (39).
(CO)5ke-
(CO)5Re
OEt
66
(CO)5Re-I
22
(CO)5Re
OEt
The sequence employing rhenium pentacarbonyl anion
(35) as a nucleophile was attempted first since the
reactions were more familiar and, in any event, the
organic reactant (65) would need to be synthesized anyway
for the sequence employing the cyclopropane (67) as a
nucleophile. It was realized that this sequence was not
on firm ground since the rhenium pentacarbonyl anion (35)
is only moderately nycleophilic18 and it would need to
attack a quaternary carbon.
Both the organic and inorganic reactants were
synthesized by literature procedures.19 The organic

30
synthesis first involved reduction and ring closure of
ethyl 3-bromopropionate (68) followed by trapping with
trimethylsilyl chloride to give 1-ethoxy-l-trimethyl-
siloxycyclopropane (70) in 57% yield.27
o Na . /° tmsci
Ei20 ^ ' OEt
This (70) was then treated with phosphorous tribromide to
generate 1-bromo-l-ethoxycyclopropane (65) in 72%
yield.28
OTMS
OEt
m
OTMS
OEt
22
PBr3
As in the case of the acyl complex, the rhenium
pentacarbonyl anion (35) was generated by reduction of
commercially available Re2(CO) 10 (34) with sodium
amalgam.
The results of mixing the rhenium pentacarbonyl anion
(35) with 1-bromo-l-ethoxycyclopropane (65) were very

31
disappointing. After periods of time ranging up to two
days, the starting organic material (65) could be
recovered unchanged. The rhenium pentacarbonyl anion
(35) is somewhat unstable, eventually going to a variety
of inorganic compounds, as evidenced by TLC, IR, and 1H
NMR.
(CO)5Re-
21
ill
No Reaction
In order to verify that the problem lay with the reaction
and not something else, the reactants were tested
separately. Since we could easily make the cyclopropyl
acyl complex (44) we knew that we were making the metal
anion (35) correctly.
A co-worker reacted the 1-bromo-l-ethoxycyclopropane
(35) with the much more nucleophilic dicarbonyl(n5-
cyclopentadienyl)iron anion (71), the result being the
desired sigma complex (72) in 25% yield.28

32
The most likely cause for the lack of reaction, then, is
insufficient nucleophilicity of the rhenium pentacarbonyl
anion (35).
This failure was disappointing, although not entirely
surprising. We next turned our attention to the use of
the 1-ethoxycyclopropyl anion (67) as a nucleophile. The
syntheses of the reactants were again relatively simple.
Treatment of Re2(CO)10 (34) with I2 results in (CO)5Re-I
(39).20 Treatment of 1-bromo-l-ethoxycyclopropane (65)
with tert-butyllithium is known to give the metal
exchanged product (67).28 To our surprise, there was no
reaction when the two were mixed. The (CO)5Re-I (39)
could be recovered after reaction times of up to two
days.
(CO)sRe-I
22
No Reaction
A literature investigation indicated that (CO)5Re-I
(39) had not been the most favorable system to try this
reaction on. It has been shown that when CH3Li is mixed
with (CO)5Re-I (39) displacement of the iodide to give

33
the methyl sigma complex (42) does not occur. The
isolated product is the acetyl-iodo rhenium anion (73).20
CH3Li
(CO)5Re-I
12
CO O
I y>-CH3
OC Re—I
Li+
OC
/
CO
21
Indeed, if two equivalents of methyllithium are added to
the same reagent (39) and then the product protonated,
the resulting compound is the bis hydroxycarbene (74).30
(CO)jRe-I
12
1) 2 CHiLi
2) H+
CO 9H
l/CHJ
OC— Re—I
/
OC
HO
24
The literature also reports that if one of the
terminal COs is replaced by a phosphine then the
substitution of the halide in 75 by a methyl group may be
accomplished easily to give 76.2-'-

34
CO
l/°
OC Re— Br
/ \
OC pph3
CH3Li
CO
I CO
I /
OC— Re—CH3
/.
OC pph3
7¿
76
The phosphine substituted rhenium halide (75) was
synthesized according to literature procedures in 21%
yield (literature yield 52%).32
Br2
Re,(CO)10 - (CO)5Re-Br
CC14
34
PPh3
CHClj
(PPh3)(CO)4Re-Br
11
The reaction with 1-lithio-l-ethoxycyclopropane (67) was
carried out. Unfortunately, the results were the same.
The starting rhenium reagent (75) could be recovered
unchanged after two days of reaction.
In order to rule out the possibility that the 1-
lithio-l-ethoxycyclopropane (67) was not being generated

35
at all, the same procedure that had been used previously
to generate it was performed and then benzaldehyde was
added. After protonation and work up the resulting
alcohol (77) was isolated in 67% yield.
22
At this point we were forced to abandon the choice of
cyclopropane as the strained ring to undergo
rearrangement. Our attempts to form the sigma complex
(66) directly were fruitless. Although we were
successful at forming the acyl complex (44), it would not
decarbonylate to form the sigma complex (45) or carbene
complex (46).
The most reasonable alternative to the cyclopropane
system was the cyclobutane system. The reaction scheme
we chose is shown below.

36
There were three reasons for this choice. The first is
that experiments with the analogous dicarbonyl(n5-
cyclopentadienyl)iron system (81) have shown that the
rearrangement of interest can occur in the cyclobutyl
system.13
The second reason was that it was hoped that the
cyclobutyl ring would migrate from the acyl carbon to the
iron to form a sigma complex more easily due to its more
normal ring bonds.
The last reason is that the necessary organic acyl
chloride (87) was known and may be made easily.13

37
co2h
M
DUDA
2) 02
3) NaHS03
OH
CO2H
8S
NaH
CH3I
OCH3
co2h
J o
<
SI
The synthesis of the starting
accomplished in 52% yield without
acyl complex
incident.
(78) was

o
ia
'll (c6n6)
u>
03
parts per million
Figure 5: XH NMR of Pentacarbonyl(1-methoxycyclobutyl-
1-carbonyl)rhenium(78)

o
OCH-i
(COkRc
la
13C |1111 (UX I
X
X
1 1 » 1—
w
VD
300
250
100
Figure 6:
200 150
parts per million
13C NMR of Pentacarbonyl(1-methoxycyclobutyl-
1-carbonyl)rhenium(78)
50

Figure 7: IR of Pentacarbonyl(1-methoxycyclobutyl-l-
carbonyl)rhenium(78)

41
Upon thermolyis in toluene at 105°C, however, the
reaction did not go as expected. Thermolysis yielded
several products, all in poor yield. The mixture of
products was very difficult to separate. After many
attempts at column chromatography we gave up trying to
purify the mixture. Some information, however, could be
gleaned from the results. The large amount of gas
evolution observed combined with the observation of peaks
in the vinylic region of the 1H NMR spectrum and the lack
of a characteristic peak very far downfield in the 13C
NMR spectrum indicate that a probable sequence involves
decarbonylation, formation of the desired sigma complex,
and then decomposition via eliminations and ring opening
reactions of the cyclobutane ring. The absence of the
peak far downfield in the 13C spectrum indicated that the
desired carbene complex (80) was not present within the
limits of detection. The 1H NMR spectrum did not
indicate the presence of either methoxycyclobutane (88)
or 1-methoxycyclobutene (89). After this we abandoned
hope of obtaining the carbene (80) via thermolysis. We
turned our attention to photolysis.
It was hoped that the reason for the decomposition
was the large amount of energy available at this high
temperature. It was believed that by doing the

42
decarbonylation photochemically at lower temperature the
sigma complex (79) would not have enough energy to
decompose as it had at higher temperature in the
thermolyses.
The results of the photolyses in deuterated benzene
indicated that these expectations were partially correct.
They indicate that the decarbonylation and rearrangement
to the sigma complex did take place successfully. It did
not react further in the same way that it had under
thermolytic conditions. Instead the sigma complex
reacted further in a very interesting and unexpected way.
The products obtained were characterized by ^-H NMR,
FT-IR, GC-MS, and comparison to the reported properties
of the known compounds.33,34 The organic products were
shown to be a nearly 1:1 mixture of methoxycyclobutane
(88) and 1-methoxycyclobutene (89) . The inorganic
product was determined to be almost exclusively dirhenium
decacarbonyl (34).
Reo(CO)io
och3
+
£&
och3
M
8£

H
parts per million
Figure 8: Photolysis of Pentacarbonyl(1-methoxy-
cyclobutyl-1-carbonyl)rhenium(78)

44
There were two possible mechanisms that were
considered to explain this observation. They both start
with the decarbonylation of the acyl complex (78) and
subsequent rearrangement to the desired sigma complex
(79). The two mechanisms then diverge. The first
mechanism relies on beta hydrogen abstraction by the
metal to generate the products. The second relies on a
radical pathway to produce them.
The overall scheme of the beta hydride abstraction
mechanism is as follows:
och3
L(CO)4Re-H + |
21
£2
och3
(CO)4Re
22
och3
Re2(CO)10_nLn + p
och3
(CO)5Re-
-CO
och3
\
(CO)4Re—
22
H
There are two variants of the radical process, a
chain mechanism and a non-chain mechanism. An overview
of the non-chain mechanism is as follows:

45
och3
V
23
och3
V
22
och3
(CO)5Re + X
52
I 23
Re2(CO)10
2A

46
The steps in the chain mechanism are very similar to
those in the non-chain mechanism:
OCH,
0CH3
(CO),
G
light
(CO)5Re
55
79
21
och3
(CO)5Re-
22
(CO)5Re
55
£2
(CO)5Re-H
94
OCH3
v
(CO)5Re +
55 SS

47
The first step in the beta hydride abstraction is
proposed to be dissociation of a CO from the sigma
complex (79) to form a 16e“ intermediate (95). This
intermediate could either pick up a ligand from solution
or abstract a beta hydrogen to give a methoxycyclobutene
pi complex containing a metal hydrogen bond (90 or 98).
och3
(CO)5Re
-CO
79
OCH3
(CO)4Re
25
och3
L(CO)4Re
26
och3
(CO)4Rc —
H
20
och3
L(CO)3Re
22
och3
L(CO)3Re—
H
28
This type of rearrangement has been shown to occur in the
analogous dicarbonyl(n5-cyclopentadienyl)iron system
(99).13

48
22
CO'
OCH3
m
The pi complex could then expel the 1-methoxycyclobutene
(89) and replace it with a ligand from solution to give a
hydride complex (91 or 103).
och3
(CO)4Re — [_
H
2Q
L L(CO)4Re-H
21
och3
V
£2
och3
L(CO)3Re
L LjCCO^Re-H
m
och3
H
102
S2

49
This hydrido complex (91 or 103) would then attack a
molecule of 1-methoxycyclobutane sigma complex (104) to
generate methoxycyclobutane (88) and the metal dimer
(106).35
LM(CO)5.MRe-H +
21 M=1
10? M=2
OCH3
(CO)*, Re
104 N=4,5
OCH3
\1_
+ Re2(CO))0.MLM
fifi
The other mechanism involves the homolytic cleavage
of the acyl (78) or sigma complex (79) to generate the
rhenium pentacarbonyl radical (55) and the
methoxycyclobutyl radical (93). The rhenium
pentacarbonyl radical (55) could then abstract a hydrogen
from a molecule of the sigma complex (79) to generate
methoxycyclobutene (89), (CO)5Re-H (94), and another
rhenium pentacarbonyl radical (55).

50
OCHj
(CO)jRe
22
light
(CO)5Re
55
, och3
(CO)5Re
79
och3
/
â–¡
22
och3
+
22
(CO)5Re +
55
och3
V
+
£2
(CO)5Re-H
24
In the non-chain mechanism the rhenium pentacarbonyl
radical (55) abstracts a hydrogen from the
methoxycyclobutyl radical (93) to generate the metal
hydride (94) and 1-methoxycyclobutene (89).
och3
(CO)5Re
22
light
(CO)5Re
55
+
och3
/
(CO)5Re-H
24
+
och3
\
£2
22

51
The hydride (94) could then react with another molecule
of the 1-methoxycyclobutyl sigma complex (104)36 or the
methoxycyclobutyl radical (93) to generate
methoxycyclobutane (88).
och3
(CO)5Re-H + (CO)NRe-
94
OCH3
Re2(CO)5+N +
104
(CO)5Re-H
24
och3
r4
OCh
\
3
+
â–¡
92
22
M
In an effort to determine which scheme is the more
nearly correct, several experiments were carried out.
They fell into two basic areas. The first of these
concerned deuterium incorporation during photolysis in
deuterated solvents. The second involved observation of
the changes induced in the photolysis by the presence of
added reagents.
The products of the photolyses in deuterated benzene
and especially deuterated toluene were analyzed carefully
by 1H NMR and GC-MS and there was no evidence for

52
deuterium incorporation. This was especially important
for the hydrogen on carbon 1 of methoxycyclobutane (88)
since it must come from some intermolecular source. It
would seem reasonable that if this were a radical
mechanism and it were carried out in deuteriotoluene,
there would be some incorporation of the deuterium into
the products. This speaks against the radical mechanism,
but is obviously only negative evidence.
The second area of investigation concerned the
effects of added phosphines on the photolysis. When one
equivalent of triethylphosphine is present during the
photolysis, two significant changes are observed. First,
one can actually observe the presence of a metallohydride
in the NMR spectrum. The hydride that is observed is
the one substituted by two phosphine ligands (105).
co
PEt3
oc Re—H
1Q¿
Second, the ratio of methoxycyclobutane (88) to 1-
methoxycyclobutene (89) is no longer roughly 1:1. In the
initial stages of the reaction there is as much as a 5

53
fold excess of 1-methoxycyclobutene (89) over
methoxycyclobutane (88).
H
och3
££
1 :
och3
/
+
(PEt3)2(CO)3Re-H
££
IQS
5
As the photolysis is continued, the amount of the
metallohydride (105) present decreases and the ratio of
methoxycyclobutane (88) to 1-methoxycyclobutene (89)
returns to nearly 1:1. Towards the end of the photolysis
trace amounts of hydride substituted with a single
phosphine are detected. The number of phosphine ligands
present on a metallohydride is easily determined due to
the fact that phosphorus has a spin of 1/2. The net
result is that the presence of one phosphorus on the
metallohydride splits the far upfield peak in the 1H NMR
spectrum (5 to 6 ppm upfield from TMS) from the hydride
into a doublet and the presence of two phosphorus ligands
splits the hydride signal into a triplet.

54
Replacing the triethylphosphine with triphenyl-
phosphine or trimethylphosphite results in significantly
different, although related, results. The
triphenylphosphine acted almost as if it weren't there.
Although detectable, the hydride never built up to a very
high concentration and the ratio between
methoxycyclobutane (88) and 1-methoxycyclobutene (89) was
unchanged as the reaction progressed. The presence of
trimethylphosphite resulted in a very rapid growth of the
peaks due to the hydride and then an equally rapid
decrease. This also left the ratio of methoxycyclobutane
(88) to 1-methoxycyclobutene (89) unchanged. A
reasonable explanation for this is that the
triphenylphosphine is not taken up during the reaction
and the trimethylphosphite is, but the hydride
substituted with two molecules of trimethylphosphite
reacts rapidly to generate the methoxycyclobutane and
metal dimer.
All of the mechanisms presented above can account for
these observations. In the beta hydride abstraction
mechanism a simple way to account for this is to have the
addition of one triethylphosphine be faster than the
rearrangement of the acyl complex (78) to the sigma
complex (79).

55
The second phosphine replaces the 1-methoxycyclobutene
(in 108) to form the diphosphine metallohydride (105)
which then slowly reduces the sigma complex (79) to give
the metal dimer (106) and methoxycyclobutane (88).
och3
v
PEi3(CO)3Re
H
PEt
3
(PEt3)2(CO)3Re-H
im
och3
/
£2
108

56
Either radical mechanism can account for this simply by
having the rhenium pentacarbonyl radical (55) substitute
two phosphines, the second more rapidly than the first.
There is literature precedent for the rapid exchange of
phosphines on radical centers, with different phosphines
substituting at different rates and with differing
amounts of mono- and di-substitution.37
(CO)5Re * 2 PEi3 (PEi3)(CO)4Re (PEt3)2(CO)3Re
55 m Ufl
To distinguish between radical and non radical
mechanisms two samples of the 1-methoxycyclobutyl-l-
carbonylrheniumpentacarbonyl (78) were photolyzed in
benzene in the presence of triphenylmethane and p-methoxy
phenol, respectively. It was hoped that these compounds
would donate hydrogen atoms to any 1-methoxycyclobutyl
radicals (93)present, thus increasing the ratio of
methoxycyclobutane (88) to 1-methoxycyclobutene (89).
The triphenylmethane had no effect. The ratio remained
at roughly 1:1. In contrast, photolysis in the presence
of 5 fold excess of p-methoxy phenol resulted in a large
increase in the amount of methoxycyclobutane (88). The
final ratio was 4.3:1 in favor of methoxycyclobutane

57
(88). This is very strong evidence in favor of the
presence of the methoxycyclobutyl radical in the
solution, supporting the radical mechanism. There was no
reaction of the p-methoxyphenol with the acyl complex
(78) in the absence of photolysis. In addition, it will
be shown later that p-methoxyphenol does not react with a
complex that is very similar to sigma 79, the only
difference being that the cyclobutane ring is
benzannelated (i.e. complex 130). This indicates that p-
methoxyphenol is not a strong enough acid to form
methoxycyclobutane (88) in the absence of a radical
reaction.
Qualitatively the rate of the reaction was not
affected by the presence of p-methoxyphenol. If the
chain mechanism were operating, one would expect a
decrease in the rate of reaction.

58
This would come about as a result of the trapping of
the rhenium pentacarbonyl radical (55) to give the
hydride (94). Since the radical (55) is the chain
propagating agent, the chain would neccessarily be
broken. The lack of an observable rate decrease speaks
strongly against a chain mechanism.
It has been shown by Heinekey and Graham38 that 7-
carbonylcycloheptatrienerhenium pentacarbonyl (111) may
be decarbonylated to the corresponding sigma complex
(112) by photolysis in deuterated acetone at low
temperature.
We decided to follow his example and also expand on
it. We carried out photolyses of the methoxycyclobutyl
acyl complex (78) not only in deutero acetone at -65°C,
but also at room temperature and in deuterated toluene at
-65°C to try to synthesize the sigma complex (79) . The

59
products were characterized by 1H NMR and also GC-MS. At
room temperature the organic products of the photolysis
in deuterated acetone were characteristic of a free
radical mechanism.
o
tight
(CD3)2CO
Room temp.
0CH3
+
OCH3
S£
§9
+ MeOH
62
+
OH
ch3o
C—CD3
I
cd3
m

60
Since this did not result in the desired product, we
cooled the sample to -65°C during the photolysis of the
acyl complex (78) in deuterated acetone. This gave only
three organic products. These products were 1-
methoxycyclobutene (89), methoxycyclobutane (88), and 1-
methoxycyclobutanecarboxaldehyde (115) in a 1:0.56:0.40
ratio, again products typical of a free radical reaction
H
och3
M
0.56
och3
y
+
S2
1 0.40
The low temperature (-65°C) photolysis was repeated
except in deuterated toluene* The products were the
same. The amount of methoxycyclobutane (88)could not be
determined due to overlap of its methoxy signal with
unreacted starting material (78) . The ratio of aldehyde
(115) to alkene (89) was 0.5:1.

61
H
OCH3
SB
0CH3
/
89
1
A reasonable explanation for the observation of the
aldehyde (115) at low temperature is that at room
temperature after absorption of the first photon and loss
of CO the migration of the cyclobutyl group to the metal
center is relatively fast. By the time the photon comes
which converts the molecule to radicals, the molecule is
already a sigma complex (79). The radicals, hence, are
the rhenium pentacarbonyl radical (55) and the 1-
methoxycyclobutyl radical (93). At low temperature,
however, the migration is not nearly so fast. After the
ejection of the CO the methoxycyclobutyl group does not
migrate to the metal immediately. This allows time for
the ejected CO to return to the vacant site. The low
temperature would also aid this process due to the
decrease of rates of diffusion near the vacant site,
increasing the length of time the CO spends in the
vicinity of the metal and hence increasing the
probability of return. This decreases the efficiency of

62
the decarbonylation and increases the probability that a
relatively inefficient process that depends on the
concentration of the acyl complex (78) (i.e. homolysis to
generate radicals 116 and 55) will become significant.
(CO)5Re +
55
OCH3 0
S
m

63
In addition, the photolysis of the cyclobutyl acyl
(78) was performed under 6.3 atmospheres of CO at room
temperature in C5D5. There were no observed changes in
either the rate of reaction or the products (i.e.,
methoxycyclobutane (88) and 1-methoxycyclobutene (89))
compared to an identical sample photolyzed side-by-side
with the CO pressurized sample except under 1 atmosphere
of N2. This is consistent with the product forming
reaction being faster than the reaction of 106 with CO.
At this point we felt we had enough information to
make a reasonable postulate as to what was happening.
Upon photolysis the vast majority of the photons which
were absorbed resulted in the ejection of a molecule of
CO. At room temperature the cyclobutyl group migrated
rapidly to the metal center. At low temperature there
was only partial migration. The next productive reaction
was the homolysis of the Re-C bond through absorption of
another photon to generate the metal radical (55) and
either the methoxycyclobutyl radical (93) (at room
temperature) or the methoxycyclobutyl acyl radical (116)
(at low temperature). This brings up an interesting
point: why (at room temperature) is the first productive
reaction upon absorption of light the ejection of CO and
the second productive reaction upon absorption of light

64
the loss of the alkyl radical? It seems unlikely that
the electronic structure of the rhenium pentacarbonyl
moiety is so drastically different when it has an alkyl
ligand attached compared to when it has an acyl ligand
attached that there is no loss of CO in the alkyl case
and all photons cause homolysis to the radicals. The
upshot is that there is probably loss of CO from the
alkyl case, but it comes back in to the vacant site.
This is important since it points out that the cyclobutyl
ring did not rearrange to form a carbene even though
there was a vacant coordination site present to permit
it. This indicates that the rearrangement was either
endothermic or had a high energy of activation. We
decided to lower the energy of the desired carbene
complex. If the lack of rearrangement was due to the
rearrangement being endothermic, this change might induce
the formation of the desired carbene. If the problem lay
in the activation energy, this change might help also due
to the Hammond postulate.
Just as an electron-donating group on a carbene
carbon stabilizes the complex, it has been shown that
replacement of a CO on a metal complex by a phosphine
also stabilizes the complex.39 We decided to replace one
of the CO's on the cyclobutyl acyl complex (78) with a

65
triethylphosphine group and compare its (107) reactivity
with that of the analogous unsubstituted complex (78).
This substitution was accomplished by simply heating
the unsubstituted acyl (78) with 1 equivalent of
triethylphosphine in benzene for 6 hours at 70°C.
The reactivity, unfortunately, was exactly the same
as before the substitution. Thermolysis resulted in a
very complex mixture of products. The 13C NMR spectrum
did not show the presence of the characteristic low field
peak indicative of a carbene carbon. The photolysis in
benzene produced a mixture of methoxycyclobutane (88) and
1-methoxycyclobutene (89) in a roughly 1:1 ratio.

66
The photolysis in deuterated acetone at -65°C gave
1-methoxycyclobutene (89), methoxycyclobutane (88), and
l-methoxycyclobutanecarboxaldehyde (115) in a 1:0.42:0.47
ratio.
o
Light
(CD3)2CO
-65 °C
och3
-och3
och3
6
1
H
££
£2
115
0.42
: 1.0
0.47
A mechanism which incorporates all of the data is as
follows:

67
och3
(CO)5Re
79
(CO)5Re
51
22
PEt3
Fast
(PEt3)2(CO)3Re
108
22
(PEt3)2(CO)3Re-H
mi
+
£2
S&
Re^CO^PEt^
112

o
68
(CO)5Re
55
OCH
/
3
22
OCH-,
(CO)sRe-H
2á
£2
OCH,
22
OCH,
\!
Re2(CO)10
2á
S£

69
och3
OCHj
(CO)5Re + \
55 I
+ (CO)5Re
55
£9
+ (CO)5Re-H
24

70
(CO)5:
(CO)5Re
Re'
OCH,
OCH,
Light
Acetone-Dft
(CO)5Re -
-65 °C
21
OCH,
(CO)5Re -
22
22
OCH,
. (CO)5Re +
55
22
OCH,
52
och3
X
aa
(CO)5Re-H
24
ns
(CO)5Re +
25
115
52

71
The direct methods of forming a carbene complex from
a cyclobutyl complex were obviously not giving the
desired results. An indirect method was sought which
might allow a system to undergo a rearrangement of the
type under study. An effort was made to put the
possibility of beta hydride abstraction to our advantage.
It has been shown in the iron system that the trans beta
methoxy cyclobutyl sigma complex (120) will, upon loss of
CO, isomerize to the alpha methoxy sigma complex (99) and
then rearrange to the carbene complex (83).13
22
SI
It was hoped that the analogous rhenium pentacarbonyl
complex (121) would undergo similar rearrangements.

72
(CO)5Re
OCH3
121
(CO)4Re
122
OCH3
(CO)4Re
och3
H
2Q
och3
(CO)4Re
25
(CO)4Re
och3
m
There is one major advantage to using this indirect
pathway. It stems from the fact that we were unable to
isolate any alpha methoxy sigma complex (79) from the
previous work. This indicates that it (79) is either a
highly reactive species which decompose to something
other than the desired carbene complexes or was never
formed. The mechanistic results detailed previously
(e.g. the formation at room temperature of
methoxycyclobutane (88) and 1-methoxycyclobutene (89) but
no 1-methoxycyclobutanecarboxaldehyde (115)) argue that
the sigma complex (79) is formed. If sigma complex 79 is
formed it decomposes to compounds other than the desired
carbene comlex (80). The advantage of the above scheme
is that once the alpha methoxy sigma complex (95) is
formed in the indirect pathway there is already a vacant

73
coordination site on the rhenium. It was hoped that this
would increase the probability of the rearrangement to a
carbene (80) happening as opposed to decomposition
pathways.
The synthetic strategy involved the reaction of
cyclobutene epoxide (123) with rhenium pentacarbonyl
anion (35) followed by trapping by CH3I.
(CO),Re- +
21
m
(CO)jRe
124
CH3I
(CO)5Re
OCH3
121
The cyclobutene epoxide (123) was synthesized by
literature methods. The first step involved the
reduction of commercially available cyclopropane
carboxylic acid (125) with LiAlH4 to the alcohol (126).40
LiAlH,
ch2oh
121
The second step was isomerization of the cyclopropyl
carbinol (126) to cyclobutanol (127) via acid
catalysis.^9 This compound (127) was then converted to

the tosylate (128) by reaction with tosyl chloride in
pyridine.39
H+
OH
TsG
■•bhgun
h2o
Pyndine
1 2(j
127
128
OTs
The tosylate (128) was then treated with potassium
t-butoxide in DMSO to form cyclobutene (129). The
cyclobutene (129) was collected and bubbled through
a -20°C solution of m-chloroperoxybenzoic acid in CH2Cl2.
This mixture was then stirred for 3 days at 0°C. The
solvent was carefully removed by Vigreaux distillation.
The final purification of the cyclobutene epoxide (123)
was accomplished by preparative gas chromatography.^1
o
OTs
KOlBu
[=1
mCPBA /_\
DMSO
' 1 1
CH2C12 1
128
-20°C
122
The results of the addition of rhenium pentacarbonyl
anion (35) to the cyclobutene epoxide (123) followed by
trapping with methyl iodide were very disappointing. The
only isolated organometalic product was (CO)5Re-CH3, and

75
this was only in trace amounts. Apparently the
nucleophilicity of the rhenium pentacarbonyl anion (35)
is not sufficient to open up the epoxide (123). The
anion (35) simply does not react and slowly decomposes.
The small amount that remained eventually attacked the
methyl iodide.
A short summary of the major points of this project
is in order. The first attempt involved the use of 1-
alkoxy substituted cyclopropane (44) to achieve the
desired rearrangement. The requisite sigma complex (45)
could not be formed from the acyl complex (44). The 1-
ethoxycyclopropyl sigma complex (66) could not be formed
either via nucleophilic attack on a rhenium halide (39,
76) or from nucleophilic attack of a rhenium
pentacarbonyl anion (35) on 1-bromo-l-ethoxycyclopropane
(65) .
The decarbonylation of the 1-methoxycyclopropyl acyl
complex (44) resulted in homolytic cleavage of the Re-C
bond. This was attributed to the reluctance of the
cyclopropane to migrate to vacant coordination sites on
the metal.

76
The attempt to solve the problem of the lack of
migration from acyl to alkyl by going to the 4 membered
ring seems to have been successful.
This brought with it a different problem. The metal
seemed to be removing a beta hydrogen from the sigma
complex (79) during radical decomposition.
Before we had conclusively found that the mechanism
of decomposition was via radicals, we searched for a
system which would be immune to the problems encountered
previously. It must not involve a cyclopropane, it must
have a methoxy in the alpha position, and either have no
beta hydrogens or beta hydrogens which, if they

77
rearrange, would give a pi complex that would not
dissociate.
The system which was chosen satisfied all of these
requirements. This system was the 7-methoxy-7-
rheniumpentacarbonyl-benzocyclobutene system (130).
(CO)sRe
OCH3
There is obviously no cyclopropane. Molecular mechanics
calculations42 indicate that opening the 7-methoxy-
benzocyclobutene system can relieve more strain (48.5
kcal/mol) than the opening of either the methoxy-
cyclopropane (28.1 kcal/mol) or methoxycyclobutane (26.1
kcal/mol) systems. The problem of beta hydrogens is
solved elegantly. The solution to the problem lies in
the fact that if a beta hydrogen should be removed then
the product would be a methoxycyclobutadiene derivative.
If the hydrogen were removed via a beta hydrogen
abstraction then the methoxycyclobutadiene would be
complexed to rhenium (131).

78
Although cyclobutadiene complexes are known,the
cyclobutadiene moiety is complexed tightly to the metal.
We expected that the hydride ligand on the same metal
would react with the cyclobutadiene ligand to regenerate
a sigma complex (130) which would then rearrange to a
carbene complex. This would be completely analogous to
the iron pi complex (100) to sigma complex (99) to
carbene (83) series of rearrangements shown earlier.13
If the beta hydrogen were removed by a radical
process, then, assuming the same reactivity as in the
non-benzannelated case, the cyclobutadiene would be the
free molecule (132).

79
(CO)jRe
55
(CO)5Re
OCH3
â– to
(CO)5Re-H £4
(CO)5Re 15
We would not expect either of these processes to take
place due to the large amount of ring strain that would
be introduced due to the formation of the cyclobutadiene
ring. Molecular mechanics calculations42 were used to
quantify this. They indicated that converting
methoxycyclobutane (strain = 26.1 kcal/mol) to 1-
methoxycyclobutene (strain = 33.0 kcal/mol) involves an
increase of 5.9 kcal/mol in strain energy. They also
indicated that converting 7-methoxybenzocyclobutene
(strain = 48.5 kcal/mol) to 7-methoxybenzocyclobutadiene

80
(strain = 66.0 kcal/mol) involves a 17.5 kcal/mol
increase in strain energy.
Unfortunately the synthesis of the target molecule
(130) was very difficult. There were two major pathways
which were undertaken. The first involved pre-forming
the entire methoxybenzocyclobutene fragment (133) before
attaching it to the metal center.
The second pathway involved forming the benzocyclobutene
fragment (134), attaching it to the metal, then putting
the methoxy group in place.

81
9ch3
(CO)sRe
130
The former procedure was attempted first for two reasons.
The first is once a metal is involved in a reaction our
experience has shown that a wide variety of unexpected
reactions may take place. The former sequence involves
fewer steps once the metal is attached. The second
reason is that the cationic rhenium pentacarbonyl carbene
complex (137), which is critical to the sequence, is
unknown. More broadly, there are no references in the

82
literature to any cationic rhenium pentacarbonyl carbene
complexes. The analogous dicarbonyl(n5-
cyclopentadienyl)iron compound (138) has been known for
some time, however.44
The overall synthetic sequence that was begun for the
former plan is as follows:
:CBr2
Br -CN
iYY
140
Hi
139

83
OH
h2o
r —cojH
M2
l~i Base
2) 02
3) H20
OH
• COjH
The steps up through the carboxylic acid (142) are all
known from the literature. The bromobenzocyclobutene
(140) was synthesized by heating cycloheptatriene (139)
and bromoform in the presence of a base (K2CO3) and a
catalyst (18-crown-6).45

84
CHBr3 + K2C03
18-C-6
140°
f^T
140
This bromide (140) was then treated with KCN in DMSO
to replace the bromine with a nitrile (141).46 Finally,
the nitrile was hydrolyzed to the acid (142) by treatment
with KOH/EtOH/H20.47
CN
141
KOH
EtOH
HjO
79°C
— CO2H
142
The sequence from cycloheptatriene (139) to the acid
(142) was very interesting from a pragmatic point of
view. As one might expect, the first step was a very
messy reaction. There are several impurities in the same
fraction of the distillate as the bromobenzocyclobutene
(140). After repeated attempts we were able to re¬
distill the mixture and obtain pure product (140).
Unfortunately a great deal of the product was lost during

85
the purification. In order to avoid this loss, we tried
to carry the impurities along to the nitrile stage (141)
and separate them then. This was unsuccessful. The best
method by far was to carry the impurities all the way
through to the acid stage (142). All of the impurities
are considerably more volatile than the acid (142).
Simply applying a vacuum (0.01 torr, 25°C) removes all of
them, leaving the acid as a white solid.
The rest of the planned synthetic sequence was
completely analogous to that of the non-benzannelated
system (87). The introduction of the methoxy group would
be accomplished by treatment of the acid with two
equivalents of strong base followed by oxygen and work-up
to give the alcohol which could be methylated by
treatment with base and CH3I.
The introduction of the alcohol to give 143, gave an
inseparable, complex mixture. After several attempts at
direct purification we decided to carry all the compounds
through to the methoxy stage (144) and purify the mixture
then. The crude mixture was treated with NaH/Cl^I to
convert the alcohol into a methoxy group. This gave a
product mixture that was partially resolved by column
chromatography. It gave 4 mixtures of 2 major components
each. Examination by FT-IR and 13C APT spectroscopy

86
revealed that none of the 8 compounds could be the
desired alpha methoxy benzocyclobutene carboxylic acid
(144) .
At this point we reexamined the second strategy.
This involved making the benzocyclobutene acyl complex
(135), decarbonylating it to the alkyl complex (136),
converting it to the benzocyclobutenylidene carbene
complex (137), and then adding methoxide to give the
alpha methoxybenzocyclobutene sigma complex (130).
o
(CO)sRe-
136
There are two obvious problems associated with this
strategy. The first is that it requires a successful
decarbonylation from an acyl complex (135) to a sigma
complex (136) and in our hands none of our attempts had
been successful on rhenium pentacarbonyl systems. The

87
second is the intermediacy of the benzocyclobutenylidene
carbene complex (137) as mentioned above. Not only is
this not a known compound, there are to my knowledge no
known cationic rhenium pentacarbonyl carbenes. A
previous attempt to form methylidene rhenium
pentacarbonyl cationic complex was unsuccessful.48
(CO)5Re-CH3
Ph3C*BF4-
(CO)5Re-F-BF3
Finally the sequence requires that not only must the
benzocyclobutenylidene complex (137) be synthesized and
be at least moderately stable, but it must react with
methoxide to give the addition product (130).
Taking this into account we started the sequence.
The benzocyclobutene carboxylic acid (142) was treated
with oxalyl chloride to generate the corresponding acid
chloride (143). This went smoothly. Treatment of the
acid chloride (143) with rhenium pentacarbonyl anion (35)
(generated as before) gave the desired acyl (135) in a
clean reaction.

88
142
134
O
iCO)5Re‘
(CO)5Re
\ H
(CO)5Re
35
135
The acyl complex (135) was dissolved in toluene-Dg and
heated to 105°C. The thermolysis was monitored by 1H
spectroscopy. This showed that the decarbonylation went
smoothly and was complete in 90 minutes. The sigma
complex (136) decomposes only very slowly at this
temperature. This degradation is indicated by a slow
growth of peaks in the vinylic region of the 1H NMR
spectrum.
o
135

89
The next steps were more difficult. Addition of
trityl tetrafluoroborate to a methylene chloride solution
of the sigma complex (136) produces a deep red color.
This color gradually changed until after approximately
one hour the solution had become dark green. If one
follows this reaction by looking at the absorptions of
the terminal carbonyls in the IR spectrum of the mixture,
one sees a shift to higher wavenumbers after 15 minutes.
This is then followed by a change in the relative
intensities of these peaks, but no general, overall
shift. The addition of methoxide/methanol to this dark
red solution immediately changes the color to light
yellow.
Column chromatography revealed 4 types of compounds.
The first to be eluted was triphenylmethane (146). This
comes from the abstraction of a hydride by the trityl.
The yield of this is very high (e.g. 91%).
136

XTHANSUITTANCE
15 087 27 066 59 049 51 030
rf orN¿o 51gua arroRF adoino iriih n 1121.12)
U‘n
I 4
1
¡Ü21
r
1
r -»
bO
7 16
w
1 :
l
Y â– *
Y-
16 1
804
2 127
3
Y 3
67
l 1 0
2
56
6
Y -
7 1
098
2
06
2
Y -
2 1
084
2
1 1
3
Y -
5 7
396
2
73
6
Y =*
74
440
2
77
7
Y
74
453
2
79
9
Y -•
74
5 36
l
U
1
5
T -
r
6 4
73
056
1 50
2
6
3
Y -»
74
74
1 1 0
1 08
u
n l niO
Ddei
t e d
2027 0 1941 I
WAVENUUBERS (CU-1)
1856 b 17/1
(CO)bRu-
i£>
o
H6
IK (f II,( I,)
1 b 06 3
IbO I
Figure 9: IR of Benzocyclobutene-7-rhenium-
pentacarbonyl(136)

xtransuittakcc
19 324 29 139 39 953 50.2(7 (0 552 70 896
O
RE BNZO SIGUA AflER A00 IR I I fl vA/ANU lü HI (L M¿Ll ¿)
Figure 10: Reaction of Benzocyclobutene-7-rhenium-
pentacarbonyl with triphenylcarbenium
tetrafluoroborate

92
The second compound to elute is trityl methyl ether
(147). This comes from the reaction of unreacted trityl
tetrafluoroborate with methanol.
Ph3C* bf4
MeOH
PhjC-OMe + HBF4
142
The third is the desired sigma complex of alpha
methoxybenzocyclobutene (130). This comes from the
reaction of the benzocyclobutenylidene carbene (137) with
either methanol (followed by deprotonation by methoxide)
or methoxide.
+
148
122
OMe
OCHa
130

Figure 11: 1H NMR of Benzocyclobutene-7-methoxy-
7-rheniumpentacarbony1(130)

300 250 200 150 100 50 0
parta per million
Figure 12: 13C NMR of Benzocyclobutene-7-methoxy-
7-rheniumpentacarbonyl(130)

0876 17 425 34 783 52 7 00 69 43f Be 775
RE ALPHA UflllOXT BtN20(_TCL0BNI II bll.UA IN L&Ãœb
LOO ü ioOO 0 7000 O 22ÜO.O iBOO 0
AAVf NHUUE K
mi
IK (C6n6)
—t I —► ' -T
i 4Oil >i I 000. 0 BOO 00 GOO oO 40Ü m>
(CM-I)
VD
U1
Figure 13: IR of Benzocyclobutene-7-methoxy-7-
rheniumpentacarbonyl(130)

96
The fourth type of product consists of a variety of
complexes containing rhenium and terminal carbonyls.
Characterization by -^H NMR and FT-IR reveals that they
contain no protons and an abundance of terminal CO's.
They come in yellows, reds, and greens. They move at a
wide variety of speeds on the column, from very fast to
almost not at all. They contaminate all of the compounds
mentioned previously. They can only be partially
separated from the sigma complex (130) by repeated
chromatography. Fortunately they are not volatile. Very
pure sigma complex may be obtained by high vacuum (10-3
torr) low temperature (40°C) short path (< 1 cm)
distillation. Unfortunately even these mild conditions
cause the decomposition of a majority of the complex
(130).
To search for the rearrangement the thermolysis of
this compound (130) was performed in deuterated benzene
and deuterated toluene.
149

97
It was immediately apparent that this is an
exceedingly complex, sensitive, and unusual reaction.
The first time the thermolysis was performed the
results were very encouraging. There was a considerable
amount of gas evolution. The solution turned red, the
same color as the iron carbene complexes. During the
first half of the reaction the 3H NMR spectrum indicated
that it was a fairly clean reaction, characterized by the
growth of two singlets, one at 3.5 ppm and the other at
3.3 ppm. They were initially in roughly a 3:2 ratio as
expected for the methoxy and methylene peaks
respectively. The 13C NMR spectrum indicated a peak at
326 ppm. This is in the region characteristic of a
carbene carbon.
Unfortunately this carbon spectrum could not be
reproduced.
A number of interesting facts were learned during the
attempts to reproduce this reaction. Collection of the
gas evolved and analysis of it by FT-IR spectroscopy
showed only the presence of CO. When the sample (130)
was in low concentration (e.g., 20mg/ml) and the loss of
starting material followed by 1H NMR spectroscopy, the
reaction followed first order kinetics until the starting
material was approximately half consumed. The enthalpy

98
of the reaction was determined to be 21.lkcal/mol. The
entropy of activation was determined to be -2.1
cal/mol*K. At higher concentrations (e.g., 300mg/ml)
the reaction behaved in a very unusual manner. The first
five minutes of thermolysis would result in essentially
no reaction. Then after about seven few more minutes the
reaction would be 90% over, as judged by disappearance of
starting material (130). This gave the impression of
some type of catalytic decomposition with an induction
period. In an effort to determine if this was a radical
reaction, p-methoxy phenol was added to the solution.
This made no difference in the reaction.
Following the reaction by 13C NMR showed that the
reaction products change each time the reaction is
performed. Chromatography was of little help in
identifying the products. The only isolable product was
very surprising. This was the alkyl complex (136)
analogous to the starting material except that instead of
a methoxy group there is a hydrogen!
(CO)5Re-
136

99
This compound (136) shows up in most of the reactions,
ranging from only a very small amount to being the major
product. It (136) was not present at the start of the
reactions. A plausible mechanism is as follows:
co
H
This mechanism is in agreement with the negative entropy
of activation and the observed product. It does not
account, however, for the evolution of CO. The lack of

100
observance of formaldehyde may be accounted for either by
its being below the limits of detection due to this being
a minor reaction path or by loss due to reaction with
other species.
Further information may be gained from studying the
reaction by FTIR spectroscopy. This reveals that the
terminal carbonyls shift to slightly higher wavenumbers
(1933, 1901 cm-1) and, more importantly, the growth of
several peaks in the bridging carbonyl region (i.e. 1760,
1723, 1650, 1629, and 1568 cm-1). This large number of
peaks confirms the complexity of the reaction. In light
of the above mechanism and spectral evidence it should be
noted that the compound below (152) is known.49 The
ester group in it (152) absorbs at 1636 cm-1.
co
I /
Re -
CO
oc-
/I
°C CO
o
\
OCH2CH3
152
A sample of the thermolysis mixture was separated
into volatile and involatile components by vacuum
transfer. A GC-MS analysis of the volatile fraction

101
revealed only one compound, benzocyclobutenone (M.W. =
118) .
A reasonable mechanism for the formation of this compound
is beta alkyl abstraction by an unsaturated metal center.
co
I /
OC Re-
OC^ QQ
co och3
-00
130

102
The only other products which may be isolated are
rhenium compounds which contain no hydrogens and an
abundance of both bridging and terminal carbonyls. The
compound Re2(CO)10 (34) was not produced.
The results of this study conceptually parallel very
closely the results of the study on the non-benzannelated
analog. The desired sigma complex (130) was formed and
allowed to react. The molecules found alternate pathways
with lower activation energies than the one leading to
the desired carbene complexes. In the case of the
photolysis of the methoxycyclobuty1 acyl complex (78)
that pathway was radical disproportionation. In the case
of the thermolysis of the methoxybenzocyclobutenyl sigma
complex (130) there were a great many pathways. These
were non-radical pathways. They were not reproducible
and seemed to depend on concentration and temperature.
In summary, the attempt to extend the carbene
formation reaction to a different metal system than iron
failed. There is no evidence that the failure was due to
one of overall thermodynamics. The failure seems to be
due to the availability of competing decomposition
pathways.
It is suggested that future efforts concentrate on
the methoxybenzocyclobutene ligand due to the great

103
amount of strain that would be released should it open to
give the carbene.

CHAPTER 3
IRON
The next problem to be attacked was the question of
whether there really was a need for strain in addition to
an electron donating group in the alpha position to
induce the rearrangement to a carbene.
We have postulated that the rearrangement is driven
by both of these factors. It seems reasonable that if
one could increase the effect of one of these factors,
the need for the other might be diminished or even
eliminated.
We decided to test this theory by synthesizing a
molecule in which there was no ring strain and an
excellent electron donor atom to stabilize the resulting
carbene. The electron donor was chosen on the basis of
the known donating properties of the amine group as
demonstrated by earlier work done on this rearrangement
by a co-worker.13 We chose to use the dimethylamino
group. We decided to employ the same iron based metal
center as had been employed successfully by other
workersThe complete structure is shown below (153).
104

105
153
Unfortunately this would be a very difficult molecule to
synthesize directly. An indirect method was chosen. It
has been shown in other work that if one photolyzes an Fp
complex (154) which contains a trans beta amino group and
a cis hydrogen on the same carbon then the iron will
equilibrate between the alpha and beta carbons via a
sequence of hydride abstractions and replacements.13
co*
H NR2
nr2
NR2
154
155
156
CO*
nr2
157
158
N = Me, iPr

106
It was also known that addition of an amine to a pi
complex of Fp (e.g. 159) will result in formation of a
trans beta amino sigma complex (e.g. 160).13
We decided to put these facts together and create a
molecule which upon photolysis might undergo first the
rearrangement from a beta amino sigma complex to an alpha
amino sigma complex which could then rearrange to a
carbene complex. The desired structure and synthetic
sequence is shown below.

107
-H*
1¿2
láfi

108
A significant point is that when the alpha amino
sigma complex (168) is formed, it is a sixteen electron
complex. The vacant site is already present which is
required for the rearrangement to the carbene (169).
This is important since it will be only part of an
equilibrium mixture. Even if the equilibrium disfavors
the alpha amino form (168) over the beta amino form (166)
the carbene (169) may still be produced in reasonable
amounts. The reason for this is that the carbene (169)
is an eighteen electron species and hence the carbene
should be lower in energy and act as a sink to siphon off
the alpha amino form (168) from the equilibrating
mixture.
The synthesis of the propyl sigma complex (162) and
the propene pi complex (163) and the salt of the amine
(164) were accomplished according to literature
procedures without any complications.50' 51 The
synthesis of the neutral beta amino sigma complex (165)
proved considerably more interesting.
The first complication occurred when deprotonation of
the initially formed cationic sigma complex (164) was
attempted.

109
The procedure that had been employed in these
laboratories in the past was to first treat the cationic
sigma complex with K2CC>3 and then chromatograph the
product on basic alumina. The band of product resulting
from this chromatography was extremely broad. This was
unusual since chromatography of similar compounds
generally results in much narrower bands. It was also
observed that after treatment of the cationic sigma
complex (164) with carbonate and evaporation of the
solvent under vacuum the product was a very clean, yellow
solid. Our previous experience with neutral sigma
complexes lead us to expect this to be a mixture of
KHCO3, K2CO3, and an oil. The third and final
observation that made us believe something unexpected was
occurring was that the alumina needed to be basic. The
use of neutral alumina resulted in a complete lack of
neutral sigma complex (165).

110
Combining these observations, it seemed that the
deprotonation and formation of the neutral sigma complex
(165) was being accomplished on the column by the basic
alumina instead of by the K2C03. The extremely broad
band was due to the fact that the deprotonation of the
cationic sigma complex (164) was occurring as the
cationic sigma complex (164) was moved very slowly down
the column and found fresh, unreacted basic alumina. The
deprotonation then took place and the neutral sigma
complex (165) was brought guickly down the column.
A greatly improved method for the isolation of the
neutral sigma complex (165) was found. After the
addition of the dimethylamine to the pi complex (163) and
removal of the solvent, methylene chloride and basic
alumina were added to the flask containing the cationic
sigma complex (164). This was then stirred vigorously
for 5 minutes and then the entire mixture was placed on
top of a basic alumina column. The resulting band was
considerably narrower. This also helped to improve the
purity of the product since the eluting solvent need only
be polar enough to move the neutral sigma complex
(165)instead of moving the cationic sigma complex salt
(164) as before.

Figure 14: NMR of Dicarbonyl(n5-cyclopentadieny1)-
[2-(N,N-dimethylamino)prop-l-yl]iron(165)
7
0
111

Ü>5
"< i'iu ic,.i),,»
parts per mi Ilion
Figure 15: 13C NMR of Dicarbonyl(n5-cyclopentadienyl)-
[2 —(N,N-dimethy1amino)prop-1-yl]iron(165)
-L
0
112

iI
1 f>5
IK (Cfil)„)
Figure 16: IR of Dicarbonyl(n5-cyclopentadieny1)-
[2-(N,N-dimethylamino)prop-l-yl]iron(165)
400. QQ
113

114
The second complication was that the neutral sigma
complex (165) seemed to be surprisingly unstable. After
several hours at room temperature it would be largely
contaminated by a new material. The structure of the
impurity was determined to be the two diastereomers of
the chelate shown below (170):
ch3 ch3
J3L
The two possible diastereomers could only be
partially resolved through chromatography. Their
spectral characteristics are similar, as one would
expect. The absorptions of the carbonyl groups of the
two diastereomers in the infrared spectrum are at 1911,
1621 cm-1 vs 1915, 1627 cm-1. In the proton spectrum
their cyclopentadienyl groups absorb at 4.14 and 4.16
ppm. The biggest difference is in the -*-H NMR absorptions
of the N-methyl groups. One diastereomer absorbs at 2.04
ppm and 1.48 ppm while the other absorbs at 1.86 ppm and
1.63 ppm. This chelate (170) is formed much more

115
quickly during the photolysis of the sigma complex (165).
This indicates that there are two mechanisms in
operation, one thermal and one photochemical. A
reasonable mechanism for the thermal isomerization is as
follows:
The photochemical isomerization may be explained
quite simply also. A reasonable mechanism for it is as
follows:

116
170

117
The photolysis of the sigma complex (165) was
performed in deuterated benzene in an ultrasonic bath to
speed the removal of CO. This is advantageous in
decarbonylations since if the CO were to return to the
site just vacated it would be a non-productive reaction.
This should drive the reaction forward towards,
hopefully, the desired rearrangement and carbene product
(169). In spite of this, the photolysis is a very
complex reaction. Examination of the 13C spectrum in the
region of absorption of cyclopentadienyl rings shows this
very well. There are a total of 10 peaks in this region.
The major product, by far, was the dimer of the iron
fragment, Fp2• This could be isolated in 66% yield after
chromatography. By looking at the total peak heights of
the absorptions due to cyclopentadienyl rings one can
make an estimate of the amounts of the other
organometallic compounds present. Such an examination
reveals that each of these compounds represents between
2% and 10% of the total organometallic species. In
addition to the Fp2, the 13C spectrum indicates the
presence of the two diastereomers of the chelate (170).
It also indicated the presence of a very small amount of
ferrocene. The other compounds were new. It should also
be pointed out that there was a considerable amount of an

118
insoluble precipitate present. This amounted to 14% of
the weight of the starting material.
Chromatography of this mixture proved to be
difficult. This was performed under a variety of
conditions with varying results. The first method used
was chromatography on silica gel first with methylene
chloride in hexane then ethyl acetate in hexane. The
first band down the column was yellow. 1H NMR
examination showed it to be ferrocene. The second band
down the column was the iron dimer, Fp2• Following this
was a dark green band moving very slowly. In order to
speed up the chromatography the eluant was changed to
ethyl acetate. The green band immediately changed to
orange. Examination later showed it to be Fp2. The next
compounds to move down the column were the chelates
(170). At the end of the chromatography there was a
yellow band on the top of the column which had not moved.
The sudden disappearance of the green band was
intriguing. The synthesis and chromatography were
repeated except that only methylene chloride and hexane
were used as eluants. The green band came all the way
down the column, but turned orange upon leaving it! Upon
evaporation and dissolving in deuterated benzene, the 1H
NMR spectrum was almost exclusively that of Fp2. Since

119
there was no suspicion that the atmosphere in the inert
atmosphere box where the chromatography had taken place
was contaminated, it was decided to switch from silica to
basic grade III alumina to see if it would solve the
problem.
The switch did indeed solve the problem of isolation
of the green compound to a degree. The chromatography
went the same as on silica gel with only methylene
chloride and hexane as eluants. First the ferrocene was
eluted. Then the Fp2 was brought down. The green band
followed, cleanly separated. It remained green in the
recieving flask and as a solid after evaporation. Its
spectral characteristics indicated that the effort had
been worthwhile. Examination of its -*-H NMR spectrum
revealed two important facts. The first was that the
sample was not pure. There were three peaks that
correspond to cyclopentadienyl rings. One of these was
due to Fp2. The other two were unknown. The second fact
was that there was a peak 2.7 parts per million upfield
from TMS. This is in the region characteristic of methyl
groups bound to iron (e.g. 174).52

120
SHIFT = -0.5 ppm
174
Upon standing overnight in a benzene solution at room
temperature the size of this far upfield peak decreased
by about one third. This indicates that the compound is
fairly unstable and fits in well with the difficulty
observed in isolation.
Since the desired carbene complex (169) would indeed
have a methyl group bound to the iron this was very
encouraging. The next step was to obtain a 13C NMR
spectrum. This was very difficult to do due to the small
quantity of material available (20 mg). In the region of
absorptions due to cyclopentadienyl rings there were
three peaks. The largest was characteristic of Fp2. The
other two were at 87.5 ppm and 84.4 ppm. Although the
latter peak is at the same position as one of the chelate
diastereomers (170), the proton spectrum does not match
so it must be some other compound. Looking downfield in
the spectrum we see peaks at 287.2 ppm, 272.4 ppm, and

121
218.5 ppm. The peak farthest downfield is in the same
position as the corresponding cyclic iron carbene
(175).13
U1
The other two peaks are in positions appropriate for
bridging and terminal carbonyls, respectively. The fact
that there is only one absorption due to a terminal
carbonyl while at the same time two iron compounds (as
evidenced by the cyclopentadienyl absorptions) may be
explained by having the terminal CO's from both compounds
absorb at the same field.
The inference of these spectra seem to be that we
have isolated an acyclic carbene which is very unstable.
The synthesis and purification was repeated several
times with similar results. The green band could never

122
be isolated as a single material. Although the green
band was always cleanly separated from the Fp2 on the
column, there was always a large amount of Fp2 in the
sample.
In an effort to better characterize the product a
FT-IR spectrum was taken. After subtraction of the
absorptions due to Fp2 there remained a terminal CO at
1916 cm-1 and a bridging CO at 1732 cm-1. This does not
match with the presence of 2 Cp rings in the 13C spectral
data unless we assume that the absorption in the terminal
CO region is due to the overlap of 2 terminal carbonyls:
In summary, the infrared spectrum neither confirms nor
disproves the presence of a carbene complex.
Evidence for the presence of a carbene complex is
provided by the thermolysis of the sample mixture. The
sample was dissolved in deuterated benzene and warmed to
65°C. At this temperature the spectrum changed
dramatically. The cyclopentadienyl absorptions in the 1H
NMR spectrum collapsed to one large and one small peak.
The large peak was at 4.2 ppm. The small peak was at 3.6
ppm. The cyclopentadienyl region in the 13C NMR spectrum
also collapsed. The large peak was at 88.5 ppm. The
small peak was at 68.3 ppm. These peaks are
characteristic of Fp2 and ferrocene. Chromatography

123
confirmed the presence of these compounds. In a
separate experiment the volatiles were removed by vacuum
transfer. These were analyzed by GC-MS. There were
three products. We were able to identify two of them.
These were shown to be ferrocene (176) and
dimethylethylamine (177).
The presence of the amine is extremely encouraging. This
is because it is the same structure as the organic ligand
in the starting material (165) except that one methyl
group has been removed. This is exactly the skeleton
that one would obtain if the desired carbene complex
(169) had been formed.

124
Although this is certainly not conclusive, it is
consistent with the formation and decomposition of
carbene complex (169).
As was pointed out in the beginning of this paper,
theoretical calculations by Hoffmann and Berke2 predict a
facile equilibrium between carbenes with alkyl groups on
the metal (e.g. 6) and the unsaturated isomer (e.g.5) in
which the alkyl group has migrated to the carbene carbon.
co
oc Mrn— CH2-CH3
oc^co
CH3 CO
1/
oc— M n=CH2
cx/to
i
£
This equilibrium was demonstrated by Stenstrom when he
placed a methoxy carbene complex (83) under CO pressure
and trapped a sigma complex (120).13

125
+C0
120
OCH3
It has recently been shown in these laboratories by
Patton that the analogous dimethylamine carbene complex
(175) is inert to 5 atmospheres of CO over a period of
several days. Presumably this is due to the greater
stabilization of the carbene form by the better electron
donor dimethylamine.

126
No Reaction
If the alkyl group on the iron were to migrate to the
carbene carbon not only would the stabilization of the
carbene by the dimethylamine be lost, but a strained
four-membered ring would be created.
In contrast to this in the case of an acyclic carbene
(e.g. 169) there would be no strain to inhibit the
migration of the alkyl group to the carbene carbon. It
was predicted that the acyclic carbene complex (169)
would react more readily with CO via the 16 electron
complex (168). In light of this CO was bubbled through
the dark green solution containing the carbene. There
was an immediate reaction. Within 10 seconds the dark
green solution was changed into a dark red one. The
product was not the expected sigma complex, however. The
only product that could be isolated was Fp2. This was
unfortunate, but it is still very significant that the
green compound did react with CO rapidly at room
temperature. This is consistent with the compound being

127
the carbene (169) that was the synthetic target. This
also implies that the carbene (169) is in rapid
equilibrium with the unsaturated isomer (168).
169 ^
To summarize the work on the iron system: A dark
green iron complex was produced by the photolysis of a
beta amino sigma complex.
The very low field absorption in the 13C NMR (287 ppm)
spectrum and the very high field resonance in the 1H NMR
spectrum (2.7 ppm above TMS) suggest that it is an amine
stabilized carbene complex with a methyl group on the
iron. Due to the inability to obtain pure samples of the
compound it could not be fully characterized. The
complex was very unstable, decomposing to Fp2 on standing
in benzene. Upon warming this complex generates Fp2 and
N,N-dimethylethylamine. The complex reacts immediately
with CO at 1 atmosphere to generate Fp2 and unidentified
organics.

128
Consideration of this evidence leads to the
conclusion that the carbene compex (169) may have been
synthesized from the unstrained sigma complex (165), but
it is very unstable. Further characterization is needed,
although this will probably have to be done through the
formation of derivatives.
165
169

CHAPTER 4
CONCLUSION
This research has demonstrated that one must deal not
only with thermodynamics but also kinetics when examining
a reaction.
The research on the rhenium systems did not result in
the synthesis of the desired carbenes due to the
availability of side reactions which went faster than the
formation of the carbene complexes. As was described in
the introduction the product carbenes, if they had been
formed, should have been stable. This would arise from
the very similar rhenium carbonyl complexes which have
been fully characterized. In the cyclopropyl and
cyclobutyl systems this side reaction was cleavage to the
radicals. In the benzocyclobutyl system there seem to be
a variety of side reactions available. They are probably
not radical pathways as shown by the fact that the
reaction is unaffected by the presence of p-methoxy-
phenol. This is a strong indication, though certainly
not a proof.
The study of these side reactions, especially
concerning the conversion of the cyclobutyl system into
methoxycyclobutane and 1-methoxycyclobutene, was very
exciting from a mechanistic point of view. The study of
this reaction provided a great deal of information on the
129

130
mechanism of such radical processes, in particular those
involving phosphine substitutions and hydride transfers.
The iron system demonstrated the difficulty
encountered when dealing with unstable species. By
eliminating the strained ring the inhibition against the
migration of the alkyl group to the carbene carbon was
lost. The product carbene (169) was characterized
spectroscopically, through its reactivity with CO, and
its thermal decomposition products.
Further research into the attempt to form a carbene
by alkyl migration from a carbon to a metal other than Fe
will be very difficult to direct clearly. Although the
thermodynamics of the rearrangement are fairly clear, the
kinetics of the possible decomposition pathways are not.
Keeping these properties in mind, a likely candidate
might be (176):
116

131
The thermodynamics should be similar to the rhenium
pentacarbonyl system. The kinetics of decomposition are
unknown but the pathways should be considerably different
due to the different substituents on the metal.
For the non-strained rearrangement the obvious type
of system to try would be one which had two good electron
donors on the alpha carbon (177). This will stabilize
the carbene even more than the single dimethylamine
employed in this study and the enhanced stability should
allow more complete characterization.
X = OMe. NMe^
177

CHAPTER 5
EXPERIMENTAL
Hexane and tetrahydrofuran were distilled from sodium
potassium alloy with an indicator of benzophenone ketyl.
Methylene chloride was distilled from p4O10 under
nitrogen. Silica gel was either Matheson, Coleman, and
Bell or Alfa 230-400 mesh. Alumina was Brockman 80-200
mesh activity I which was deactivated to activity III by
the addition of 6% (w/w) water. Both silica gel and
alumina were degassed overnight (0.1 mm Hg, 25°C) prior
to use. NMR spectra were taken on a JEOL FX-100 (100 MHz
for proton and 25 MHz for carbon), or on a Varian XL-200
(200 MHz for proton and 50 MHz for carbon). Results are
reported in parts per million downfield from internal
tetramethylsilane. Infrared spectra were recorded on
Nicolet 5-DXB FTIR or on a Perkin-Elmer 283-B
spectrometers. Elemental analyses were performed by
Atlantic Microlab Inc. or University of Florida
analytical services. Melting points (uncorrected) were
obtained on a Thomas Hoover apparatus. All solutions
containing metals were consistantly manipulated under
inert atmosphere (Schlenk tube or glove box) conditions
employing purified nitrogen.
132

133
Preparation of 1-Methoxy-l-thiophenylcyclopropanef51)
This compound was prepared according to the method of
Cohen, Bhupathy, and Matz.23 A solution of 1.95g (0.0130
moles) thiophenylcyclopropane in 20ml THF was prepared
and cooled to 0°C. To this was added 7.7ml of 2.59M
nBuLi (0.02 moles) in hexanes over a period of 30
minutes. This mixture was allowed to stir for 4.5 hours
at 0°C then 30 minutes at 25°C. The solution was then
cooled to -78°C and a solution of 6.lg I2 in 25ml of THF
was added. The solution became very viscous. While
still at -78°C a solution of 2g Na2S2C>3 in 20ml of H20
was added. The dark characteristic color of I2
disappeared. The reaction mixture was stirred at -78°C
for 30 minutes then at 25°C for 30 minutes. The mixture
was poured into a separatory funnel and 300ml of H20 was
added. This mixture was extracted with 3 100ml portions
of ether. The extracts were combined and dried over
MgS04. The solvent was removed under vacuum. A
suspension of 4g Na2C03 in 100ml of methanol was added to
the residue. The mixture was refluxed for 4 hours. The
suspension was then placed in a separatory funnel and
300ml of H20 were added. The solution was extracted with
3 100ml portions of CH2C12. The solution was dried over
MgS04 and the solvent removed under vacuum. The product

134
was distilled on a kugelrohr apparatus at 75 - 80°C and
0.3 torr (lit. 70 - 75°C at 0.2 torr) . The product
weighed 1.99g (0.0110 moles, 85% yield). NMR (CDCI3,
100 MHz) 7.8 - 7.4 (M, 5H, Phenyl), 3.5 (S, 3H,
Methoxy), 1.4 - 1.2 (M, 4H, Methylenes)
Preparation of 1-Methoxvcyclopropane Carboxylic Acid (53)
This compound was prepared following the general
procedure of Lisko and Jones.A 500ml, 3 neck round
bottom flask was charged with 0.24g finely divided Li,
4.3g naphthalene (0.034 moles), and 250ml THF. The flask
was fitted with 2 septa and an all glass mechanical
stirrer. The mixture was stirred for 20 hours. During
this time the solution turned green and most of the Li
went into solution. The solution was cooled to -78°C and
a solution of 3.Og (0.017 moles) 1-methoxy-l-
thiophenylcyclopropane (51) in 10ml THF was added via
transfer needle. The mixture was warmed to -25°C and
stirred for 1 hour. The solution turned to a red - brown
color. The solution was then cooled to -78°C and C02 was
bubbled through it. The solution turned colorless in
less than 1 minute. The solution was then warmed to
25°C. The pieces of Li which remained were removed with

135
a spatula. The solution was then added to 300ml of H2O.
The mixture was acidified with dilute HC1. The mixture
was then placed in a separatory funnel and extracted with
3 100ml portions of ether. The ether was then extracted
with 3 100ml portions of 5% NaOH in H20. The aqueous
extracts were combined and acidified with dilute HC1.
The solution was then extracted with 5 75ml portions of
ether. The ether extracts were combined and dried over
MgS04. The solvent was removed under vacuum on a rotary
evaporator. The residue was then distilled on a
Kugelrohr apparatus at 0.5 torr and 80 - 100°C into a
20°C trap. The product was a white solid weighing 1.3g
(0.0112 moles,67%). 1H NMR (CDCI3, 100 MHz) 11.8 (S,
1H, Acid), 3.4 (S, 3H, Methoxy), 1.4 - 1.1 (M, 4H,
Methylenes) 13C {1H} (CDCl3, 25 MHz) 198.0 (Acid), 78.9
(Quaternary cyclopropyl), 75.2 (Methoxy), 35.2
(Methylenes). IR (C6D6) 3018, 2998, 2962, 2934, 1703
cm-1 High resolution mass spectrum calculated for C5H3O3
116.04734, observed 116.0472.
Preparation of 1-Methoxvcvclopropane Carbonyl
Chloride(47) A 25ml round bottom flask was charged
with 0.812g (0.00700 moles) 1-methoxycyclopropane

136
carboxylic acid (53). To this was added slowly 4.4g
(0.035 moles) of oxalyl chloride. The mixture was
allowed to stir under nitrogen for 18 hours. The mixture
was then distilled on a kugelrohr apparatus at 70 torr
and 90 - 100°C. The product was collected in a 25°C
trap. The product weighed 0.415g (44%). 1H NMR (CDC13,
100 MHz) 3.38 (S, 3H, Methoxy), 1.7 - 1.3 (M, 4H,
Methylenes)
Preparation of Pentacarbonyl(l-methoxycvclopropyl-l-
carbonyl) rhenium C44) A solution of 0.5 g Re2(CO)10 in
100 ml dry, 02 free THF was prepared. This was syringed
onto an amalgam consisting of 1.1 g Na and 140 g Hg. The
mixture was stirred at room temperature for 4 hours.
After this time the red solution was placed via transfer
needle in a 250 ml round bottom flask containing a stir
bar. To this was added slowly at room temperature a
solution of 0.3 g of 1-methoxycyclopropane carbonyl
chloride (47) in 10 ml THF. This mixture was allowed to
stir overnight. Then 2 ml of silica gel was added and
the solvent was removed under vacuum. The resulting
powder was placed on a 1" x 5" silica gel column and
eluted with 200 ml of hexanes. This fraction contained

137
unreacted Re2(CO)3Q an<3 was discarded. The solvent was
then changed to 3% ethyl acetate in hexanes and a yellow
band was eluted. Removal of the solvent under vacuum
resulted in the isolation of the yellow acyl complex.
0.35 g 52% Analytical samples may be obtained by
recrystallization from hexane. M. P. 80.5° - 81.5°
NMR ((CD3)2C0, 100 MHz): 3.2 (3 H, singlet, methoxy),
0.8 (4 H, multiplet, cyclopropyl) 13C {1H} ((CD3)2CO, 25
MHz): 250.5 (bridging CO), 184.8 (cis CO), 183.4 (trans
CO), 83.2 (quaternary cyclopropyl), 57.2 (methoxy), 13.8
(methylene cyclopropyl) IR (CDC13): 2120, 2010, 1920,
1580 cm-1 Mass Spectrum: no M+ was observed. The major
peaks were 355 (Re(C0)g+) and 71 (methoxycyclopropyl+)
UV (hexane): nm 255 (53,000), 330 (4,400) Analysis
calculated for C10H7°7Re: c 28.24%, H 1.66%; found C
28.07%, H 1.70%
Photolysis of Pentacarbonvl(1-methoxvcvclopropyl-l-
carbonvl)rhenium (44) This reaction was performed in
C6Dg solution in an NMR tube and followed by 1H NMR
spectroscopy. Typically 0.lg of acyl complex 44 was
dissolved in 1 ml of C6D6 and 3 boiling chips were added
to the solution. A septum was placed on the NMR tube and

138
the tube was placed in an ultrasonic bath photolyzed with
a 450 watt Hanovia medium pressure lamp fitted with a
pyrex filter. The bath temperature was maintained at
22°C. The pressure in the NMR tube was maintained at 1
atmosphere by means of a N2 bubbler connected to the tube
via a needle. Very few bubbles were produced, indicating
little decarbonylation. When the reaction was complete,
as indicated by the lack of starting material (approx. 2
hours), the volatiles were removed via vacuum transfer.
The solid remaining was analyzed to be Re2C010 bY TLC (Rf
= 0.8 in hexane on silica gel) and IR (2070, 2004, 1973,
1911 cm-1). The volatile product was shown to be
compound 54, the dimer of the organic fragment, by 1H NMR
(C5D5, 100 MHz): 3.12 (3 H, singlet, methoxy), 1.4 -
0.9 (4 H, multiplet, cyclopropyl); IR (1708 cm-1); and
mass spectroscopy (30M megabore DB-1 40 - 250°C,
10°C/min, retention time 16:11 min.) (m/z = 198 (M+), 183
(M+ - CH3), 167 (M+ - 0CH3), 127 (M+ -
methoxycyclopropyl), 99 (M+ -
methoxycyclopropylcarbonyl), 71 (methoxycyclopropyl)).
Due to the volatility of this compound yields could
not be obtained through direct weighing of the product.
Examination of the methoxy peaks in the 1H NMR spectrum
indicates that this compound was formed in 95% yield.

139
The remaining compounds have peaks at 3.09, 2.90, and
2.75 and are of roughly equal areas.
Preparation of 1-Bromo-l-ethoxvcvclopropane(65) This
compound was prepared by a modification of the procedure
of R. C. Gadwood.29 A stir bar and 12 g (0.064 moles)
of 1-ethoxy-l-trimethylsiloxycyclopropane (70) were
placed in a 50 ml round bottom flask. To this was added
20 g (0.074 moles) of phosphorous tribromide. The flask
was then connected to a nitrogen bubbler and stirred for
two days. The mixture was then dissolved in 100 ml of
pentane and placed in a 250 ml separatory flask. A
saturated solution of sodium carbonate in water was added
slowly. The addition was continued until both layers
were clear after shaking. The layers were separated and
the pentane was removed under vacuum. The product was a
clear liquid which was distilled on a kugelrohr apparatus
at 70° and 30 torr (lit. 60° at 25 torr). 8.49 g (0.051
moles) 72% XH NMR (CDC13, 100 MHz) 3.6 (2H, quartet, J
= 7 Hz, ethoxy methylene), 1.2 (4H, m, cyclopropyl), 1.15
(3H, triplet, J = 7 Hz, ethoxy methyl) (lit. 1H NMR
(CC14) 3.60 (2H, q, J = 7 Hz), 1.15 (5H, m)) 13C (1H)
((CD3)2CO, 25 MHz): 74.6 (Cj), 65.8 (ethoxy methylene),

140
18.7 (cyclopropyl methylene), 14.7 (ethoxy methyl) IR
(CC14) 2980, 2960, 2930, 2883, 1740, 1720 cm"1
Preparation of 1-Ethoxv-l-trimethvlsiloxy-
cvclopropane(70) This compound was prepared by a
modification of the procedure of K. Ruhlmann.27 In an
inert atmosphere box a 500 ml, 3 neck round bottom flask
was charged with 300 ml of anhydrous ether, 13 g (0.12
moles) of trimethylsilyl chloride, 6.5 g (0.28 moles) of
finely divided sodium and a large stir bar. A solution
of 16 g (0.12 moles) of ethyl 3-chloropropionate in 50 ml
of ether was placed in an addition funnel and the funnel
was placed on top of the 3 neck flask. All openings were
closed with septa and the apparatus was brought out of
the inert atmosphere box. The apparatus was connected to
a Schlenk line through a large needle through the septum
in the addition funnel. The solution in the 3 neck flask
was stirred vigorously and the solution in the addition
funnel was added cautiously over a period of 2 - 3 hours.
The mixture was allowed to stir overnight. The mixture
was then filtered through Celite and the clear filtrate
collected. The ether was removed under vacuum. The
clear liquid remaining was distilled on a kugelrohr

141
apparatus at 65° and 20 torr (lit. 43° - 45°, 12 torr)
The product was a clear liquid weighing 11.3 g (0.067
moles) 57% (lit. 78%). 1H NMR (CDC13, 100 MHz) 3.75
(2H, quartet, J = 7.5 Hz, ethoxy), 1.2 (3H, triplet, J =
7.5 Hz, ethoxy), 0.9 (4H, singlet, cyclopropyl), 0.2 (9H,
singlet, trimethylsiloxy) 13C {^H} ((CD3)2CO, 25 MHz)
86.6 (C}), 61.6 (ethoxy methylene), 15.6 (ethoxy methyl),
14.0 (cyclopropyl methylene), 0.93 (trimethylsiloxy) IR
(CC14) 3100, 3015, 2975, 1725 cm'1
Preparation of Bromotetracarbonyltriphenylphosphine-
rhenium(75) This compound was prepared by a modification
of the procedure of P. W. Jolly and F. G. A. Stone.32 A
solution of 1.47 g (0.0022 moles) of dirhenium
decacarbonyl (34) in 26 ml of carbon tetrachloride was
placed in a 200 ml round bottom flask with a stir bar and
a septum. The flask was cooled to 0°C and a solution of
0.7 g (0.0044 moles) of bromine in 26 ml of carbon
tetrachloride was added slowly via syringe. The mixture
was then warmed to room temperature and stirred for 4
hours. The solvent was then removed under vacuum. The
solid remaining was then dissolved in a solution
containing 1.17 g (0.0045 moles) of triphenylphosphine in

142
97 ml of chloroform. This solution was then refluxed for
12 hours. The mixture was then cooled to room
temperature and the solvent was removed under vacuum.
The solid remaining was chromatographed on a 1" x 3"
silica gel column with 40% diethyl ether in hexane as the
elutant. After removal of the solvent under vacuum the
product was a white solid weighing 1.50 g (0.0023 moles)
52% M. P. 144 - 146° (lit.32 146°) 1H NMR (CDC13, 100
MHz) 8.0 - 7.4 (m, phenyl) IR (CDC13) 2103, 2001, 1945,
1812, 1792 cm'1
Preparation of Methyltetracarbonvltriphenvlphosphine-
rhenium(76) This compound was prepared according to the
method of R. J. McKinney and H. D. Kaesz.31 A solution
of 0.6 g (0.00094 moles) of bromotetracarbonyltriphenyl-
phosphinerhenium (76) in 25 ml of ether was placed in a
50 ml round bottom flask with a stir bar and sealed with
a septum. The flask was cooled to 0°. To this was added
2 ml of 1.5 M (0.003 moles) methyllithium. The mixture
was allowed to stir for 30 minutes. To this was added 3
ml of water. The layers were separated, the ether layer
was dried over MgS04 and taken to dryness under vacuum.
The solid obtained was placed on a 1" x 3" silica gel

143
column and eluted with a 10% solution of benzene in
hexane. After evaporation of the solvent the product was
a white solid weighing 0.09 g (0.00015 moles) 17% (lit.31
55%). M. P. 114.5° - 117°C 1H NMR (CDC13, 100 MHz) 7.4
-7.2 (15 H, m, aromatic), -0.6 (3 H, doublet, J = 7.4 Hz,
methyl) IR (CDC13) 2050, 1950, 1900 cm-1 (lit.
(cyclohexane) 2077, 1992, 1973, 1935 cm-1)
Preparation of (1-ethoxycyclopropyl)phenvlmethanol(77) A
solution of 0.21 g (0.0013 moles) of 1-bromo-l-
ethoxycyclopropane (65) in 10 ml of ether was placed in a
25 ml round bottom flask with a stir bar under nitrogen.
The flask was cooled to -78°C and 0.6 ml of 2.08M (0.0013
moles) t-butyllithium was added slowly via syringe. The
mixture was warmed to room temperature and stirred for 12
hours. A solution of 0.5 g of benzaldehyde (0.0047
moles) in 5 ml of ether was added. The mixture was
allowed to stir for 1 hour then 5 ml of water was added.
The ether layer was washed 3 times with aqueous sodium
bisulfite then dried with magnesium sulfate. The
magnesium sulfate was removed by filtration and then the
ether was removed under vacuum. The product was
recrystallized from pentane to give 0.164 g (0.008 moles)

144
of white crystals 67% M. P. 61° - 62°C Analysis
calculated for C-^2^16<~>2: 74.97%, H 8.39%; found C
75.20%, H 8.79%. XH NMR (CDC13, 100 MHz) 8.0 - 7.2 (5
H, m, phenyl), 4.5 (1 H, singlet, benzylic), 4.0 (1 H,
singlet, hydroxy), 3.4 (2 H, quartet, J = 6 Hz, ethoxy
methylene), 1.5 - 0.6 (7 H, m, ethoxy and cyclopropyl)
13C {%} (CDCI3, 25 MHz) 140.9 (quaternary phenyl),
127.1, 126.6, 126.2 (aromatic), 74.0 (benzylic), 64.5
(ethoxy methylene), 63.0 (quaternary cyclopropyl), 15.0
(ethoxy methyl), 9.5 (cyclopropyl methylene) IR (CC14)
3570, 3030, 2978, 2875, 1545 cm-1
Preparation of 1-Methoxvcyclobutanecarboxvlic Acid(86)
This compound was prepared according to the procedure of
Stenstrom and Jones.13 A 500ml flask was charged with
12.6g (0.125 mol) of diisopropylamine and 200ml of THF.
The solution was maintained under nitrogen and 83 ml of
1.5 M (0.125 mol) MeLi was added very slowly. A large
amount of gas was evolved. A solution of 5.0 g (0.050
mol) of cyclobutanecarboxylic acid (84) in 40 ml of THF
was added slowly via transfer needle. The mixture was
stirred for 18 hours. Dry oxygen was bubbled through the
solution for 2 hours. This was then washed with 3 50 ml

145
portions of an aqueous 20% Na2S2C>3 solution. The
extracts were then acidified with dilute HC1. This
solution was then extracted with 3 50 ml portions of
ether. The ether solution was dried with MgS04 and the
solvent was removed under vacuum. This hydroxyacid was
dissolved in 220 ml of THF. Sodium hydride (4.2g, 0.0175
mol) was added slowly. Then 25 g (176 mmol) of CH3I was
added via syringe. The mixture was stirred under
nitrogen at 25 - 30°C for 24 hours. At this time an
additional 25 g (0.0176 mol) of CH3I were added. The
mixture was then stirred at 25 - 30°C for an additional
18 hours. At this time 20 ml of an aqueous 20% solution
of Na2S2C>3 was added. The aqueous layer was then
acidified with dilute HCl. Excess NaCl was then added
and the solution extracted with 4 50 ml portions of
ether. The extracts were dried with MgS04 and the
solvent removed under vacuum. The product crystallized on
standing to give 5.4 g (0.0415 moles, 80%) of a white
solid. 1H NMR (CDCI3, 60 MHz) 9.5 (S, 1H, Acid), 3.4 (S,
3H, Methoxy), 2.7 - 1.8 (M, 6H, Methylenes) (lit. (CDC13)
10.24 (1H, s), 3.24 (3H, s), 2.5-1.8 (6H, m)

146
Preparation of PentacarbonvlÍ1-methoxvcyclobutvl-l-
carbonvl)rhenium(78) A solution of 0.5 g Re2CO^o (34)
(0.000766 moles)in 100 ml dry, 02 free THF was prepared.
This was syringed onto an amalgam consisting of 1.1 g Na
and 140 g Hg. This was stirred at room temperature for 4
hours. After this time the red solution was placed via
transfer needle in a 250 ml round bottom flask containing
a stir bar. To this was added slowly at room temperature
a solution of 0.3 g of 1-methoxycyclobutane carbonyl
chloride (0.00020 moles) (87)13 in 10 ml THF. This
mixture was allowed to stir overnight. Then 2 ml of
silica gel was added and the solvent was removed under
vacuum. The resulting powder was placed on a 1" x 5"
silica gel column and eluted with 200 ml of hexanes.
This fraction contains unreacted Re2CO10 and was
discarded. The solvent was then changed to 3% ethyl
acetate in hexanes and a yellow band was eluted. Removal
of the solvent under vacuum resulted in the isolation of
the yellow acyl complex. 0.35 g (0.000797 moles, 52%)
Analytical samples may be obtained by recrystallization
from hexane. M. P. 59° - 60°C 1H NMR (CDC13, 100 MHz)
3.18 (3 H, singlet, methoxy), 2.05 - 1.30 (6 H,
multiplet, cyclobutyl) 13C {1H} (CDC13, 25 MHz) 251.6
(bridging CO), 183.4 (cis terminal CO), 181.6 (trans CO),

147
94.3 (quaternary cyclobutyl), 50.9 (methoxy), 26.0, 11.0
(methylene cyclobutyl) IR (CC14) 2975, 2120, 1995, 1605
cm-1 Mass Spectrum: no M+ was observed. Major peaks were
355 (Re(CO)g+) and 85 (methoxycyclobutyl+) UV (hexane):
nm 255, = 53,000; 335, = 3,300. Analysis calculated
for C11H907Re: C 30.07%, H 2.06%; found C 29.89%, H
2.07%.
Photolysis of Pentacarbonylf1-methoxycvclobutvl-l-
carbonvl)rhenium (78) The general procedure is as
follows. A solution of 0.1 g ( 0.00023 moles) of complex
78 in 1 ml of CgDg in an NMR tube was prepared. Three
boiling stones were added to the tube. If the photolysis
was to be conducted in the presence of PEt3 then 1
equivalent (0.027g, 0.00023 moles) was added. The NMR
tube was sealed with a septum. The tube was placed in an
ultrasonic bath and photolyzed with a 450 watt medium
pressure hanovia lamp through a pyrex filter. The bath
temperature was maintained at 22°C. The pressure in the
NMR tube was controlled by a N2 bubbler connected to the
tube via a needle. The progress of the photolysis was
monitored by 1H spectroscopy. The disappearance of the
starting material was indicated by a decrease in the size

148
of its methoxy peak ( 3.18). The presence of
(PEt3)(CO)4Re-H (91) was indicated by a doublet (J = 28
Hz) at -5.8. The presence of (PEt3)2(CO)3Re-H (105) was
indicated by a triplet (J = 30 Hz) at -6.45. The
presence of methoxycyclobutane (88) was indicated by
peaks at 3.01 (methoxy singlet) and 3.61 (methine
multiplet). The region between 2.5 and 0 was too
complex to reliably indicate the presence of this
compound in this reaction. This data is in accord with
the spectrum reported in the literature.34 [(CCI4): 3.75
(M, 1H, Methine), 3.18 (S, 3H, Methoxy), 1.95 (M, 6H,
Methylenes)] The presence of 1-methoxycyclobutene (89)
was indicated by a multiplet at 4.40 (vinylic) and a
singlet at 3.22 (methoxy). The region between 2.5 and
0 was too complex to reliably indicate the presence of
this compound in this reaction. This data is in accord
with the spectrum reported in the literature.33 [(neat):
4.45 (M, 1H, Vinylic), 3.50 (S, 3H, Methoxy), 2.52 (M,
2H, Methylene), 2.0 (M, 2H, Methylene)] The presence of
methoxycyclobutane and 1-methoxycyclobutene was also
confirmed by GC/MS analysis which indicated m/z peaks of
86 and 84, respectively.
This photolysis was also performed using the same
procedure except using deuterated acetone as the solvent.

149
The formation of 1-methoxycyclobutene and
methoxycyclobutane were indicated by the growth of the
characteristic peaks at 4.4 and 3.7, respectively. The
major peaks in the methoxy region were at 3.44, 3.20,
3.19, 3.03, 2.93, 2.77, and 2.74. A GC-MS analysis of
the volatiles was undertaken. The separation was
performed on a 30M DB-1 Megabore column, 40°C (4
minutes)- 250°C, 10°C/min. The 1-methoxycyclobutene and
methoxycyclobutane did not separate (2 min. 46 sec.).
Their major peaks were at m/z = 86 (C5H8O, M3 + ), 84
(C5H10O, M2 + ) , 69 (M2+ ~ CH3), 56 (M^ - CH20) , and 54
(M2+ - CH20). The deuterated acetone addition product
(113) (10:58) was indicated by peaks at m/z = 132 (M+ -
CD3), 122 (M+ - C2H4), 114 (M+ - 2CD3), 104 (M+ -
(CD3)2CO), 85 (cyclobutyl), and 65 ((CD3)2COH). The
dimer of the acyl organic fragment (114) (13:30) was
indicated by m/z = 142 (M+ - methoxycyclobutene), 127 (M+
- methoxycyclobutene, methyl), 114
(methoxycyclobutanecarboxaldehyde (115)), 95, 85
(methoxycyclobutyl), 71, and 67.
This same photolysis was performed in deuterated
acetone at -65°C. Monitoring the photolysis by 1H NMR
indicated the growth of 1-
methoxycyclobutanecarboxaldehyde (115) ( 9.6), 1-

150
methoxycyclobutene (89) ( 4.4), and methoxycyclobutane
(88) ( 3.6). The major peaks in the methoxy region were
at 3.45, 3.25 (1-methoxycyclobutene (89), 3.15, 3.05
(methoxycyclobutane (88)), and 2.95 (1-
methoxycyclobutanecarboxaldehyde (115)).
This same photolysis was performed in deuterated
toluene at -65°C. Monitoring the photolysis by NMR
indicated the growth of 1-
methoxycyclobutanecarboxaldehyde (115) ( 9.5), 1-
methoxycyclobutene (89) ( 4.4), and methoxycyclobutane
(88) ( 3.6). The major peaks in the methoxy region were
at 3.25 (1-methoxycyclobutene (89)), 3.03
(methoxycyclobutane (88)), and 2.87 (1-
methoxycyclobutanecarboxaldehyde (115)).
Preparation of cis-Triethylphosphinetetracarbonvl-1-
carbonvl(1-methoxvcvclobutvl)rhenium f107) A solution of
0.0529 g (0.000121 moles) of pentacarbonyl-l-carbonyl(1-
methoxycyclobutyl)rhenium in 1 ml C6D6 was prepared in an
NMR tube. To this was added 0.04 g (0.00034 moles) of
triethylphosphine. The NMR tube was capped with a septum
and heated to 70°C for 12 hours. At this time the
solvent was removed under vacuum and the residue

151
chromatographed on silica gel (20% EtOAc/Hexanes). The
yellow product band was collected and the solvent removed
under vacuum. The product was a yellow oil weighing
0.0523 g (0.0000988 moles, 82%). 1H NMR (C6D6, 100 MHz):
3.18 (3 H, singlet, methoxy), 2.4 - 2.2 (6 H, multiplet,
cyclobutyl), 2.8 - 2.5 (2 H, multiplet, methylene of
PEt3), 1.0 - 0.5 (3 H, multiplet, methyl of PEt3).
13C{1H) (CDC13, 25 MHz): 262.9 (doublet, J = 9.8 Hz,
bridging carbonyl), 190.4 (doublet, J = 9.8 Hz, carbonyls
cis to both PEt3 and bridging CO), 188.6 (doublet, J =
7.3 Hz, carbonyl trans to bridging CO), 187.8 (doublet, J
= 29 Hz, carbonyl trans to PEt3), 94.2 (quaternary
cyclobutyl), 50.7 (methoxy), 26.2 (methylenes next to
quaternary cyclobutyl), 18.6 (doublet, J = 29 Hz,
methylene on PEt3), 17.0 (methylene of cyclobutyl), 7.73
(methyl of PEt3). Mass spectrum (Re has two isotopes,
185 and 187): 502, 500 (M+ - CO), 474, 472 (M+ - 2C0),
445, 443 (M+ - methoxycyclobutyl), 417, 415 (M+ -
methoxycyclobutyl and CO). UV (hexane) 243 nm, = 23,000;
300 nm, = 1,100; 370 nm, = 250.
Photolysis of cis-Triethvlphosphinetetracarbonvl-1-
carbonvl(1-methoxvcyclobutvl)rhenium(107) A solution
151

152
of 0.01 g of complex 118 in 1 ml of CgDg in an NMR tube
was prepared. Three boiling stones were added to the
tube. The NMR tube was sealed with a septum. The tube
was placed in an ultrasonic bath and photolyzed with a
450 watt medium pressure hanovia lamp through a pyrex
filter. The bath temperature was maintained at 22°C.
The pressure in the NMR tube was controlled by a N2
bubbler connected to the tube via a needle. The progress
of the photolysis was monitored by spectroscopy. The
disappearance of the starting material was indicated by a
decrease in the size of its methoxy peak ( 3.18). The
presence of methoxycyclobutane (88) was indicated by
peaks at 3.01 (methoxy singlet) and 3.61 (methine
multiplet). The region between 2.5 and 0 was too
complex to reliably indicate the presence of this
compound in this reaction. This data is in accord with
the spectrum reported in the literature.34 [(CC14): 3.75
(M, 1H, Methine), 3.18 (S, 3H, Methoxy), 1.95 (M, 6H,
Methylenes)] The presence of 1-methoxycyclobutene (89)
was indicated by a multiplet at 4.40 (vinylic) and a
singlet at 3.22 (methoxy). The region between 2.5 and
0 was too complex to reliably indicate the presence of
this compound in this reaction. This data is in accord
with the spectrum reported in the literature.33 [(neat):
152

153
4.45 (M, 1H, Vinylic), 3.50 (S, 3H, Methoxy), 2.52 (M,
2H, Methylene), 2.0 (M, 2H, Methylene)]
Preparation of Cvclopropylcarbonol (126) This
compound was prepared by a modification of the method of
McCloskey and Coleman.40 A solution of 20.2 g (0.0230
mol) of cyclopropane carboxylic acid in 300 ml of
anyhdrous ether was prepared in a 500 ml, 3 neck round
bottom flask. A large magnetic stir bar was added and a
dry ice/ acetone condenser was placed on top. To this
was added 10 g (0.0130 mol) LiAlH4 very slowly with
vigorous stirring. The mixture was allowed to stir for 1
hour after the addition was complete. The remaining
LÍAIH4 was quenched by the very slow addition of 50 ml of
H20. The mixture was then filtered through Celite. The
filter cake was washed with 50 ml of H20 and 50 ml of
ether. The water and ether were separated in a
separatory funnel. The water was saturated with NaCl and
a continuous extraction was performed on it with ether
for 18 hours. The ether from the continuous extraction
was combined with the ether from the separatory funnel.
The combined ether solutions were dried with MgS04. The
ether was then distilled off with a vigreaux column. The

154
residue was distilled on a kugelrohr apparatus at 70°C
and 90 torr into a 0°C trap (lit 123 -124°C, 738 torr).
The product was a clear liquid weighing 15.5 g (0.0215
mol, 92%) 1H NMR (CDC13, 60 MHz) 3.4 (D, J = 7HZ, 2H,
CH20H), 3.1 (S, 1H, Hydroxy), 1.4 - 0.8 (M, 1H,
Methine), 0.8 - 0.1 (M, 4H, Cyclopropyl methylenes). IR
(CDCI3) 3300, 3080, 1820, 1795, 1660 cm"1
Preparation of Cvclobutanol(127) This compound was
prepared according to the method of Fadel, Saloun, and
Conia.40 To a mixture of 20 ml of concentrated HCl in
100 ml of H20 was added 15.5 g (0.0215 mol) of
cyclopropylcarbinol. This was connected to a mercury
pressure release and refluxed for 18 hours. The solution
was then cooled to room temperature and neutralized first
by the addition of NaOH and then NaHC03. The solution
was then saturated with NaCl and a continuous extraction
with ether was performed for 18 hours. The ether was
then removed by distillation using a vigreaux column.
The residue was distilled on a kugelrohr apparatus at
100°C and 70 torr into a 0°C trap (lit40 123°C at 733
torr). The product was a clear liquid which weighed 12.0
g (166 mmol, 77%). 1H NMR (CDC13, 60 MHz) 4.2 (M, 1H,
154

155
Methine), 3.2 (S, 1H, Hydroxy), 2.3 - 1.0 (M, 6H,
Methylenes) (lit. (CC14) 4.46 (s, OH), 4.18 (p, 1H, J =
7.5 Hz), 2.5 - 0.8 (m, 6H)). IR (CC14) 3300, 2940, 2800,
1550 cm"1
Preparation of Cvclobutvl Tosylate(128) This compound
was prepared according to the method of Fadel, Saloun,
and Conia.40 A solution of 5.3 g (0.073 mol) of
cyclobutanol in 30 ml of dry pyridine was prepared. To
this was added 22 g (0.0110 mol) of tosyl chloride. The
mixture was stirred at 0°C for 3 hours and then put in a
refrigerator at 5°C for 3 days. The solid was then
collected on a sintered frit. The solution was washed
with 50 ml of ether and then 2M HCl until there was no
more odor of pyridine. The ether was removed under
vacuum. The yellow liquid remaining was then
chromatographed on a 1" x 3" silica gel column with 30%
methylene chloride in hexane. The solvent was removed
under vacuum. The product was a clear liquid which
weighed 12.4 g (0.055 mol, 75%) XH NMR (CDC13, 60 MHz)
7.9 - 7.2 (M, 4H, Phenyls), 5.0 - 4.4 (M, 1H, Methine),
2.3 (S, 3H, Methyl), 2.2 - 1.2 (M, 6H, Methylenes) (lit.
(CC14) 7.76 (2H, d, J = 8.3 Hz), 7.34 (2H, d, J = 8.3

156
Hz), 4.76 (1H, p, J = 7.5 Hz), 2.48 (3H, s), 2.8 - 1.1
(6H, m) . 13C {1H} ((CD3)2CO, 25 MHz) 145.3, 134.9
(Ipso), 130.6, 128.2 (Aromatic Methines), 74.6
(Cyclobutyl Methine), 31.3 (Methyl), 21.7, 13.4
(Methylenes). IR (CDC13) 2950, 2850, 1930, 1590, 1050
cm--'-
Preparation of Cvclobutene Epoxide(123) This compound
was prepared according to the method of Ripoll and
Conia.41 A 250 ml, 3 neck round bottom flask was fitted
with a magnetic stir bar, a condenser, and a pressure
equalized dropping funnel. The flask was then charged
with 14 g (0.0125 mol) of potassium t-butoxide and 150 ml
of DMSO. A solution of 7.3 g (0.032 mol) of cyclobutyl
tosylate in 15 ml of DMSO was placed in the dropping
funnel. Next to this flask was placed a 500 ml, 3 neck
flask fitted with a pressure equalized dropping funnel, a
stir bar, and a dry ice/ acetone condenser. To this flask
was added 150 ml of CH2C12. A solution of 9.5 g (0.055
mol) of 80% m-chloroperoxybenzoic acid in 100 ml of
CH2C12 was placed in this dropping funnel. Septa were
placed on both dropping funnels, the unused neck on the
CH2C12 flask and the condenser on the DMSO flask. The

157
available neck on the DMSO flask was fitted with a
nitrogen inlet. The opening on the dry ice condenser was
fitted with a nitrogen outlet. The septum on top of the
condenser on the DMSO flask was connected to the
condenser on the unused neck on the CH2Cl2 flask by a
transfer needle. The end of the needle extended below
the level of the CH2C12. The CH2CI2 flask and the
attached dry ice/ acetone condenser were cooled to -78°C.
The DMSO flask was heated to 70°C. The solution of
cyclobutyl tosylate was allowed to drip into the
potassium t-butoxide solution over a period of 1 hour.
Nitrogen was flushed through the system in order to carry
the cyclobutene being formed in the DMSO flask into the
CH2Cl2 flask. After the addition was complete the black
DMSO mixture was allowed to stir at 70°C for 2 hours. At
the end of this time the nitrogen flow was stopped and
the transfer needle removed. The CH2C12 was then warmed
to -10°C. The m-chloroperoxybenzoic acid solution was
then added slowly. A cold finger was then placed in the
dry ice/ acetone condenser which maintained its
temperature at -35°C. The flask was then warmed to 0°C
and maintained at that temperature for 3 days. At the
end of this time all volatiles were collected by vacuum
transfer. The majority of the CH2Cl2 was removed by

158
vigreaux distillation. The final purification was
performed by preparative GC on a 1/4" by 18' SE-30 column
at 70°C. The product was a clear liquid weighing 0.79g
(0.011 moles, 35%) (lit.41 51%) B. P. 64°C. 1H NMR
(CDC13, 100 MHz) 3.79 (M, 2H, Methines), 2.2 - 1.4 (M,
4H, methylenes) (lit. (CCl4) 3.69 (d, J = 2 Hz), 2.3 -
1.5). 13C {1H) ((CD3)2CO, 25 MHz) 54.5 (Methines),
28.4 (Methylenes). IR (CDC13) 3060, 2990, 2940, 2840
cm-1
Preparation of 7-Bromobenzocvclobutene(140) This
compound was prepared by the method of DeCamp and
Viscogliosi.46 In a 500 ml round bottom flask was
combined 129 g (1.4 moles) cycloheptatriene, 119 g CHBr3
(0.476 moles), 71 g K2C03 (0.5 moles), and 3.5 g 18-C-6.
This mixture was heated to 140°C for 10 hours. The
product was then distilled using a vigreaux column. The
fraction boiling in the range 55 - 65°C at 1 torr was
collected (lit. 48-51°, 0.75 torr). The product weighed
14.8g (0.08 moles, 17%) (lit. 26%) 1H NMR (CDC13, 100
MHz) 7.4 - 6.9 (m, 4H, aromatics), 5.15 (1H, doublet of
doublets, = 2.0 Hz, J2 = 4.5 Hz, H next to Br), 3.62
(1H, doublet of doublets, J± = 4.5 Hz, J2 = 14.6 Hz,

159
methylene H trans to Br), 3.20 (1H, doublet of doublets,
J-L = 2.1 Hz, J2 = 14.8 Hz, methylene H cis to Br) 13C
{1H} (CDCI3, 25 NHz) 145.9, 141.9 (quaternary
aromatics), 130.1, 128.1, 123.3, 122.5 (aromatics), 43.8
(CH2), 41.9 (CH). IR (CDCl3) 3072, 2935, 2250, 1745,
1459, 872 cm-1.
Preparation of 7-Cvanobenzocyclobutene(141) This
compound was prepared by a modified method of Cava, Litle
and Napier47 in 79% yield (lit. 93%). The modification
consisted of purification of the product by
chromatography (silica gel, 20% ethyl acetate in hexane)
instead of distillation under reduced pressure. 1H NMR
(CDCI3, 100 MHz) 7.4 - 7.0 (m, 4H, aromatic) 4.25 (1H,
doublet of doublets, Jj = 4.0 Hz, J2 = 4.0 Hz, H next to
CN) 3.60 (1H, d, J = 5.8 Hz, H trans to CN) 3.54 (1H, d,
J = 2.3 Hz, H cis to CN) 13C {1H} (CDCl3, 25 MHz) 190.84
(CN), 142.30, 138.40 (quaternary aromatic) 128.36,
127.29, 122.52, 121.44 (aromatic), 35.38 (CH2), 27.98
(CH) IR (CDCl3) 3075, 2983, 2944, 2254, 2246, 1460,
1430 cm-1.

160
Preparation of Benzocvclobutene-7-carboxvlic Acidfl42)47
A solution consisting of 60 ml of water, 60 ml of
ethanol, and 20 g of potassium hydroxide was prepared.
To this was added 11.2g (0.087 mole) of 7-
cyanobenzocyclobutene (141). This mixture was heated to
80°C for 3 hours. The solution was then cooled to room
temperature. To this was added 200ml of water that had
been saturated with sodium chloride. This was then
extracted with ether (3x75ml) and the organic layer
discarded. The agueous layer was acidified with 3N HC1
then extracted with ether (3x75ml). The ether layer was
dried over magnesium sulfate. The magnesium sulfate was
removed by filtration and the solution taken to dryness
under vacuum. The product was a white solid weighing
5.6g (0.038 mole, 43%). 1H NMR (CDC13, 100 MHz) 10.3
(1H, broad, OH), 7.4 - 6.9 (4H, m, aromatic), 4.26 (1H,
t, J = 4.1 Hz, H next to carboxylate), 3.39 (2H, d, J =
4.1 Hz, methylene) 13C {1H} (CDC13, 25 MHz) 179.0
(carboxylate), 143.96, 142.01 (quaternary aromatic),
128.32, 127.39, 122.86, 122.47 (aromatic), 45.62
(methine), 33.87 (methylene) IR (CDC13) 3000 (broad),
1707 (strong, broad), 1459, 1416, 1306, 1225 cm-1

161
Preparation of Benzocvclobutene-7-carbonvl chlorideC143)
A round bottom flask was placed under nitrogen and a
magnetic stir bar was added. Then 5.6 g (0.043 moles) of
benzocyclobutene-7-carboxylic acid (142) was added. To
this was added 20 ml (28 g, 0.22 moles) dropwise over 5
minutes. This mixture was stirred at room temperature
overnight. The solution was then distilled on a
kugelrohr apparatus at 90° and 1 torr. The product was
collected in a 25° water bath and the excess oxalyl
chloride was collected in a -78° trap. The product
weighed 5.9 g (0.035 moles, 82%). 1H NMR (CDCI3, 100
MHz) 7.3 - 6.8 (M, 4H, Aromatics), 4.6 - 4.4 (M, 1H,
Methine), 3.4 - 3.3 (M, 2H, Methylene). 13C (1H) (CDC13,
25 MHz) 172.1 (carbonyl chloride), 143.0, 140.7
(quaternary aromatic), 129.2, 127.8, 123.2, 122.7
(aromatic), 56.0 (methine), 37.7 (methylene) High
resolution mass spectrum calculated for C9H701C11:
166.01826, observed 166.01852.
Preparation of Benzocvclobutene-7-carbonvlrhenium-
pentacarbonvl(135) In a 3 neck, 250 ml round bottom
flask was placed 125 g mercury and a stir bar. To this
were added 10 pieces of sodium, each weighing 0.1 g.

162
This was done under a stream of nitrogen. The flask was
then placed in an ice water bath. Then a solution of 1 g
Re2CO10 (34) (0.00153 moles) in 125 ml of tetrahydrofuran
was added via transfer needle over a period of 30
minutes. The stir bar was allowed to rotate only very
slowly, 1-2 RPS. After the addition was complete the
flask was placed in a room temperature water bath. The
reduction was then allowed to proceed for 2 hours.19
After this time the reddish-orange tetrahydrofuran
solution was transferred back to its original flask via
transfer needle. The solution was stirred rapidly and a
solution of 0.55 g (0.0033 moles) of benzocyclobutene-7-
carbonyl chloride (143) in 5 ml of tetrahydrofuran was
added via transfer needle. The reddish color disappeared
and the solution became yellow and cloudy. After 5
minutes the solvent was removed under vacuum. The yellow
solid was chromatographed on a 1" x 4" silica gel column.
The chromatography was performed with a 2% ethyl
acetate/hexane elutant. The product was a yellow solid
weighing 0.73 g (0.00160 moles, 52%). The solid melted
under nitrogen at 113-115° with the evolution of bubbles.
Analysis (calculated) C 36.76%, H 1.54% (found) C 36.65%,
H 1.56%. 1H NMR (CDC13, 100 MHz) 7.2 - 6.8 (4H, m,
aromatic), 4.28 (1H, doublet of doublets, J-^ = 3.6 Hz, J2

163
= 5.0 Hz, methine), 3.22 (1H, d, J = 1.8 Hz, methylene
cis to carbonyl), 3.18 (1H, d, J = 5.0 Hz, methylene
trans to carbonyl) 13C {1H} (CDC13, 25 MHz) 244.3
(bridging CO), 183.0 (cis terminal COs), 180.9 (trans
terminal CO), 144.6, 142.6 (guaternary aromatics), 127.5,
127.0, 122.4, 122.3 (aromatics), 76.0 (methine), 32.5
(methylene) IR (CDC13) 2928, 2135, 2066, 2048, 2012,
1600, 1004, 598 cm-1 high resolution mass spectrum, m/e
calculated (M+- 2CO) 401.98741, found 401.98882
Preparation of benzocvclobutene-7-rhenium-
pentacarbonvl(136) A solution of 0.47g (0.0010 moles)
enzocyclobutene-7-carbonylrheniumpentacarbonyl (135) in
5ml of toluene was prepared under nitrogen. This
solution was heated to 105°C for 90 minutes. There was a
great deal of bubbling, especially during the early
stages of the thermolysis, indicating loss of CO. After
this time period the solution was cooled to room
temperature and the solvent was removed under vacuum.
The yellow oil remaining was chromatographed on silica
gel using 2 % Ethyl Acetate in hexane. The product moved
with the solvent front. The product was a colorless
solid weighing 0.3817g (0.00089 moles 86%). It had a

164
melting point of 35-36°C under Nitrogen. Analysis
calculated for C^HyC^Re: C 36.36%; H 1.64%. Found: C
36.43%; H 1.68%. 1H NMR (C6D6, 100 MHz) 7.0 - 6.5 (4H,
m, aromatic), 3.5 - 3.3 (2H, m, methylene), 3.1 - 2.8
(1H, m, methine) 13C {1H} (C6D6, 25 MHz) 185.03 (cis
COs), 180.94 (trans CO), 162.15, 142.70 (quaternary
aromatics), 127.04, 124.48, 122.56, 120.31 (aromatic),
44.07 (methylene), 10.0 (methine) IR (CH2Cl2) 2157,
2127, 2055, 2013, 1982 cm-1 High resolution mass
spectrum, m/e calculated 429.98511, found 429.98592
Preparation of Benzocvclobutene-7-roethoxy-7-rhenium-
pentacarbonyl(130) To a 100 ml round bottom flask was
added 0.255g (0.000594 moles) of benzocyclobutene-7-
rheniumpentacarbonyl (136) and 30 ml of methylene
chloride. This was cooled to -78°C and a solution of
0.196g (0.000589 moles)of triphenylcarbenium
tetrafluoroborate in 10 ml of methylene chloride was
added via transfer needle over a period of 10 minutes.
After the addition was complete the flask was placed in
a 25°C water bath and allowed to stir for 20 minutes.
During this time the solution changed from yellow to a
very dark red. A solution of 0.032g of sodium methoxide

165
in methanol was then added rapidly via transfer needle.
The color changed immediately to yellow and the solution
became cloudy. This was allowed to stir for 5 minutes
then the solvent was removed under vacuum. The resulting
yellow oil-solid mixture was placed on a l"x4" silica gel
column and chromatographed with 30% methylene chloride in
hexane. There are two yellow bands that come down with
this elutant. The product is contained in the slower
moving band (0.065g, 24%).
An analytically pure sample may be obtained by an
extremely short path ( Hg). The product thus obtained is a colorless semi-solid
at room temperature which freezes completely on cooling
to -30°C. Analysis calculated for C^HgOgRe: C 36.60%; H
1.97% Found C 36.57%; H 2.02%. 1H NMR (C6D6, 100 MHz)
7.1 - 6.9 (4H, m, aromatic), 3.73 (1H, d, J = 14.7 Hz,
CH), 3.37 (1H, d, J = 14.7 Hz, CH) 13C {1H} (C6D6, 25
MHz) 185.9 (cis COs), 181.5 (trans CO), 159.7, 139.5
(quaternary aromatic), 129.4, 128.9, 127.8, 125.3
(aromatic), 76.6 (quaternary aliphatic), 52.6 (methoxy),
50.2 (methylene) IR (C6D6) 2963, 2946, 2887, 2129, 2059,
2017, 1982 cm-1 UV (hexane) 280 nm, = 9,200; 340 nm, =
6400.

166
Thermolysis of Benzocvclobutene-7-methoxv-7-rhenium
pentacarbonvl (130) This thermolysis was performed in
C6Dg solution in an NMR tube. The pressure in the NMR
tube was maintained at 1 atmosphere by means of a N2
bubbler. The thermolysis was performed at 60°C and was
complete in 15 minutes. When the starting material was
in low concentration (e. g. 0.01 g/ 1 ml solvent) the
reaction was followed by -*-H NMR spectroscopy. The
progress of the reaction was most conveniently followed
by observing the decrease of the peak from the methoxy
group in the starting material. In the initial stages of
the reaction this decrease was concurrent with the growth
of two new peaks in the methoxy region ( 3.83 and 3.65).
As the reaction progressed these peaks were joined by a
large number of other peaks in the same region, resulting
in a broad, complex pattern ( 4.5 - 3.0). When the
starting material was in high concentration (e. g. 0.3 g/
1 ml solvent) the reaction was followed by 13C
spectroscopy. Concurrent with the disappearance of the
peaks due to the starting material was the growth of a
large number of peaks. These peaks were at 196.5,
185.2*, 181.2*, 161.2*, 160.9, 144.6, 142.8*, 129.9,
128.6, 126.5, 125.5, 124.9*, 122.6*, 120.4*, 87.4, 57.2,
52.0, 49.3, 44.2*, and 10.8*. Those peaks marked with an

167
asterisk. (*) correspond to benzocyclobutene-7-
rheniumpentacarbonyl (135). After the thermolysis was
complete the infrared spectrum of the solution was
obtained. The spectrum showed that peaks at 3460, 2102,
2036, 1933, 1901, 1760, 1723, 1650, 1629, and 1568 cm'1
had grown in. During the course of the thermolysis large
amounts of gas were evolved. This gas was sampled. Its
infrared spectrum indicated the presence of CO. There
was no correspondance when compared to a sample of
gaseous formaldehyde generated through the thermolysis of
paraformaldehyde. The GC-MS spectrum of the volatile
components of this thermolysis was taken on a SPB-1
column from 40 - 170°C at 10°C/min. There was only one
peak due to a reaction product. It indicated the
presence of benzocyclobutenone due the peak at 4:33 min
(m/z = 118 (M+), 90 (M+ - CO), and 89 (M+ - H, CO)).
Preparation of Dicarbonvl-in—-cvclopentadienyl)fl¬
or opvl)iron(162) This compound was prepared by the
general method of M. L. H. Greene and P. L. I. Nagy.51
5.0 g (0.023 moles) of potassium dicarbonyl-(n5-
cyclopentadienyl)ferrate was suspended in approximately
50 ml of THF in a 100 ml round bottom flask with vigorous

168
stirring. A solution of 1.8 g (0.0229 moles) of 1-
chloropropane in 20 ml of THF was added via transfer
needle over 10 minutes. After the addition was complete
the mixture was allowed to stir for 10 minutes. The
solvent was then removed under vacuum. Then 5 g of
silica gel was added and the mixture was placed on top of
a 1" x 5" silica gel column and eluted with hexane. The
product moves down rapidly as a yellow band. Removal of
solvent yielded 3.4 g (0.0155 moles, 67%) of a yellow
oil. 1H NMR (C6D6, 100 MHz) 4.07 (5 H, s, Cp), 1.6 -
0.9 (7 H, m, alkyl) 13C (1H) ((CD3)2CO, 25 MHz) 218.4
(CO), 86.0 (Cp), 32.1 (Cx), 20.1 (C3), 7.7 (C2) IR
(CH2C12) 1940, 1995 cm-1 (lit. (neat) 2013, 1953 cm-1)
Preparation of Dicarbonvl-(n—-cvclopentadienvl)-
(propenvl)iron tetrafluoroborate(163) This compound was
prepared according to the method of M. L. H. Greene and
P. L. I. Nagy.51 A solution of 3.4 g (0.0155 moles)
dicarbonyl-(n5-cyclopentadienyl)(propyl)iron (162) in 30
ml of methylene chloride in a 250 ml round bottom flask.
This solution was cooled to 0°C. A solution of 5.1 g
triphenylcarbenium tetrafluoroborate (0.0155 moles) in 50
ml of methylene chloride was added over 15 minutes via

169
transfer needle. The mixture was stirred at 0° for 30
minutes. The mixture was then warmed to 25°C and stirred
for an additional 30 minutes. 50 ml of ether were added.
The resulting precipitate was filtered and washed with 2
x 20 ml portions of ether. The product was a yellow
solid weighing 4.3 g (0.014 moles, 91%). 1H NMR (CD3CN,
100 MHz) 5.51 (5H, s, cyclopentadieny1), 5.2 - 4.8 (1H,
m, secondary vinyl), 3.77 (1H, d, J = 8.3 Hz, H trans to
methyl), 3.40 (1 H, d, J = 14.4 Hz, H cis to methyl) IR
(CH2C12) 2075, 2036 cm-1 (lit. 2089, 2055 cm'1)
Preparation of Dicarbonvl(n—-cvclopentadienvl) r2-(N,N-
dimethylamino)prop-l-yl1 iron f165) Approximately 10 ml
dry degassed acetonitrile was vacuum transferred to a
flask containing 1 g (0.0033 moles) dicarbonyl(n5-
cyclopentadienyl)(propenyl)iron tetrafluoroborate (163)
and a stir bar. Then 1.5 ml dimethylamine (0.03 moles)
was vacuum transferred into the same flask. The flask
was then closed and warmed to -20°C and stirred for 1
hour. The mixture was then stirred for an additional
hour at 0°C. The solvent was then removed under vacuum
at 0°C. Then 20 ml of methylene chloride and 10 ml of
basic grade III alumina were added. This mixture was

170
stirred vigorously for 5 minutes. The entire contents of
the flask were then placed on a 1" x 5" basic grade III
alumina column. Then the column was eluted with 20%
methylene chloride in hexane until the red Fp2 band had
come off the column. The column was then eluted with
pure ethyl acetate until the yellow band had been
completely removed. Evaporation of the solvent yielded
0.3 g (0.00114 moles, 35%) of product. The product was
invariably contaminated with a small amount of Fp2• The
product decomposes to a significant degree during the
chromatography; repeated chromatography lowered yields
and did not lead to an increase in purity. Acceptable
elemental analyses could not be obtained. NMR (CgDg,
100 MHz) 4.18 (5 H, s, cyclopentadienyl), 2.5 - 2.3
(1 H, m, H2), 2.14 (6 H, s, N,N dimethyl), 1.00 (3 H, d,
J = 6.1 Hz, H3) 13C (l-H) (C6D6, 25 MHz) 218.4 (CO),
85.3 (Cp), 64.6 (C3), 39.9 (N,N dimethyl), 15.6 (C2), 8.6
(Cx) IR (C6D6) 2956, 2000, 1944, 863 cm-1. UV (hexane)
290 nm, = 5800. The slight heating neccessary in a mass
spectrometer caused the complex to decompose. An
acceptable mass spectrum could not be obtained. As noted
in the discussion this complex readily undergoes an
intramolecular cyclization. A high resolution mass
spectrum of the cyclized product was obtained, however.

171
Photolysis of Dicarbonvl (n-^-cvclopentadienvl) r 2-(N . N-
dimethvlamino)prop-l-vl1 iron(165). Isolation and
Characterization of Carbene Complex 169 and Chelate
Complexes 170. This photolysis was performed by
preparing a solution of 0.5 g (0.0019 moles) of sigma
complex 165 in 2 ml of C6D6 in an NMR tube. The tube was
capped with a septum and placed in an ultrasonic bath
with a 450 watt medium pressure Hanovia lamp fitted with
a pyrex filter. The sample was maintained at 22°C. The
pressure in the NMR tube was maintained at 1 atmosphere
by means of a N2 bubbler. The progress of the reaction
was monitored by both 1H and 13C NMR spectroscopy. The
1H NMR spectrum was characterized by the growth of
several broad peaks in the Cp region ( 4.5 - 3.5) and the
formation of a broad, overlapping region that covered
from 2.4 - 0.4. There were also two small peaks at 6.4
and 5.6. Of considerably more interest was the growth
of a peak at -2.4. The 13C spectrum was
characterized by the growth of a tremendous number of
peaks. The major peaks in the far downfield region were
at 287.2, a broad peak 280 - 270, a broad peak 245 -
233, 235.6, 222.4, 219.2, 218.4, and 217.7. There were
10 peaks in the Cp region. The largest by far was due to
Fp2 at 88.5. The peaks were 88.5 (Fp2, relative height

172
3430), 87.5 (carbene, relative height 453), 85.4
(relative height 265), 84.4 (chelate, relative height
751), 84.1 (relative height 270), 83.2 (relative height
190), 82.9 (chelate, relative height 182), 80.2 (relative
height 634), 79.9 (relative height 135), and 68.3
(ferrocene, relative height 300). There were far too
many peaks in the region 65 - 8 to list completely. The
larger were at 64.3, 56.5, 46.0, 40.0, 15.7, 10.8, and
8.3. Purification of this mixture was then performed
using column chromatography. The use of silica gel and
60% EtOAc in hexanes allowed the isolation of the
chelates (170) but not the carbene complex (169). The
chelates could be partially resolved through
chromatography. (CgDg, 100 MHz, Diastereomer #1):
4.16 (Cp), 2.04, 1.48 (NMe2's), 1.04 (Doublet, J = 7Hz,
C-CH3), 2.2 - 1.5 (multiplet, methine and methylene). 1H
NMR (C6D6, 100 MHz, Diastereomer #2): 4.14 (Cp), 1.86,
1.63 (NMe2's), 1.04 (Doublet, J = 7 Hz, C-CH3), 2.2 -
2.0, 1.9 - 1.2 (multiplets, methine and methylene). IR
(C6D6, Diastereomer #1): 2955, 1911, 1621, 1328, 1240
cm-1. IR (C5D5, Diastereomer #2): 2955, 1915, 1627,
1249, 863 cm-1. 13C NMR (C6D6, 25 MHz) 274.7 (bridging
CO, #2), 270.7 (bridging CO, #1), 222.9, 222.8 (terminal
CO's, could not be assigned reliably), 84.2 (Cp, #1),

173
82.9 (Cp; #2), 70.8, 65.0, 62.9, 62.5, 56.5, 55.9, 49.7,
45.9, 10.7, 9.3 (alkyls, could not be assigned reliably).
High resolution mass spectrum (mixture of diastereomers)
calculated for C12Hi7 263.06376.
Performing the chromatography on basic grade III
alumina with 40% CH2C12 allows the isolation of carbene
complex 169. This is a green, thermally unstable, very
air sensitive compound. Despite repeated attempts the
carbene comlex was always contaminated with Fp2 and one
unknown compound. The 13C{1H) (C6D6, 25 MHz) spectrum
exhibited peaks at 287.2 (carbenic carbon), 272.4
(bridging CO), 218.5 (terminal CO), 88.5 (Cp of Fp2),
87.55 (Cp), 82.3 (Cp), 70.8, 64.5, 55.0, 45.1, 16.4,
15.5, 9.0, and 1.4. IR (C6D6): 1996*, 1952*, 1916,
1781*, 1732 (Those marked with an asterisk correspond to
Fp2). 1H NMR (C6D6, 100 MHz): 4.38 (Cp), 4.22 (Cp of
Fp2), 4.01 (Cp), 2.04, 1.43, 1.38, 0.86, 0.05, and -2.7.
The peak at -2.7 was always broad. Dissolving the
sample in toluene-Dg and cooling to -80°C did not change
either the position or the breadth of this
peak. Warming the sample to 50°C in toluene-Dg did not
affect the spectrum either. At +75°C the spectrum
immediately changed to that of Fp2. A GC-MS spectrum
173

(SPB-1 column, 40 - 170°C, 10°C/min.) was taken. This
revealed the presence of dimethylethylamine (177) (m/z =
73) and ferrocene (176) (m/z = 186)
A CgDg solution of the possible carbene complex (169)
was treated with 1 Atmosphere of CO. The green color
changed to red immediately. The 1H and 13C NMR spectra
revealed only the presence of Fp2•
174

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BIOGRAPHICAL SKETCH
Paul Hanna was born on June 26, 1956, in Ft. Belvoir,
Virginia. His family moved soon and settled in
Sunnyvale, California.
He attended the University of Santa Clara and
received a bachelor's degree in June, 1978. He continued
his education at the University of Florida, receiving a
master's degree in chemistry in 1982.
179

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.
William M. Jones, 'SHairman
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.
William R. Do!bier, /
Professor of Chemistry v—/
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 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.
Gus Palenik,
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.
Mural i Rao,
Professor of Mathematics
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, arid was accepted as partial fulfillment
of the requirements for the degree of Doctor of Philosophy.
Dean for Graduate Studies and
Research

UNIVERSITY OF FLORIDA
3 1262 08556 7674






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