Title Page
 Table of Contents
 Results and discussion
 Biographical sketch

Title: Synthesis and characterization of the first homoaromatic organometallic carbene complexes
Full Citation
Permanent Link: http://ufdc.ufl.edu/UF00099227/00001
 Material Information
Title: Synthesis and characterization of the first homoaromatic organometallic carbene complexes
Physical Description: vi, 83 leaves : ill. ; 28 cm.
Language: English
Creator: Radcliffe, Marc Dudley, 1953-
Copyright Date: 1982
Subject: Carbenes (Methylene compounds)   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
Thesis: Thesis (Ph. D.)--University of Florida, 1982.
Bibliography: Bibliography: leaves 80-82.
General Note: Typescript.
General Note: Vita.
Statement of Responsibility: by Marc Dudley Radcliffe.
 Record Information
Bibliographic ID: UF00099227
Volume ID: VID00001
Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
Resource Identifier: alephbibnum - 000339634
oclc - 09617123
notis - ABW9321


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Table of Contents
    Title Page
        Page i
        Page ii
    Table of Contents
        Page iii
        Page iv
        Page v
        Page vi
        Page 1
        Page 2
        Page 3
        Page 4
        Page 5
        Page 6
        Page 7
        Page 8
    Results and discussion
        Page 9
        Page 10
        Page 11
        Page 12
        Page 13
        Page 14
        Page 15
        Page 16
        Page 17
        Page 18
        Page 19
        Page 20
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        Page 25
        Page 26
        Page 27
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        Page 76
        Page 77
        Page 78
        Page 79
        Page 80
        Page 81
        Page 82
    Biographical sketch
        Page 83
        Page 84
        Page 85
        Page 86
Full Text







No acknowledgement can adequately express my gratitude to Dr.

William M. Jones, whose professional leadership and personal encourage-

ment have greatly increased the satisfaction and rewards of my graduate

studies. No past experience has offered greater intellectual freedom,

nor more equitable guidance than found here under his counsel. Moreover,

he has attracted several outstanding individuals to this research group.

William R. Winchester, Frank Manganiello and James Lisko have all contri-

buted significantly to the character of this academic experience and I am

grateful for their stimulating conversations and friendships.


ACKNOWLEDGEMENTS .............. ........ ii

ABSTRACT . . . . . .. . .. .. . ... . v


I INTRODUCTION .................... 1


III EXPERIMENTAL . . . . . . . .. . 68

General . . . . . . . . . . . 68

Cyclopentadienylirondicarbonyl Iodide ...... 69

Tri-n-butylphosphine. . . . . . . . 69

Triphenylphosphine . . . . . . .... 69

Bis(1,2-diphenylphosphino)ethane . . . ... 69

Trifluoroacetic Acid . . . . . . . .. 69

Triphenylcarbenium Hexafluorophosphate . . .. 70

Fluorosulfonic Acid . . . . . . . . 70

Potassium Cyclopentadienylirondicarbonyl . . .. 70

Bromocyclooctatetraene . . . . . . .. 70

Cyclooctatetraene Carboxylic Acid . . . ... 71

Cyclooctatetraene Acid Chloride . . . ... 71

cyclooctatetraene Carbonyl (11) . . . ... 72

Photolysis of 11 .................. .72

cyclooctatetraene (9) . . . . . .... 73

(n -Cyclopentadienylironcarbonyltri-n-butyl-
phosphine)cyclooctatetraene (12) .. . . . 74

(n -Cyclopentadienylironcarbonyltriphenyl-
phosphine)cyclooctatetraene (13) . . . ... 75

(n -Cyclopentadienyliron[bis(1,2-diphenyl-
phosphino)ethane])cyclooctatetraene (19) .... .76

n -Cyclooctatrien-1-ylium-n5 -cyclopentadienyl-
irondicarbonyl Hexafluorophosphate (10) .... .77

1 -Cyclooctatrien-1-ylium-n5-cyclopentadienyl-
ironcarbonyltri-n-butylphosphine Hexafluoro-
phosphate (17) . . . . . . . . 78

ironcarbonyltriphenylphosphine Hexafluoro-
phosphate (14) . . . . . . . . .. 79

REFERENCES . . . . . . . .. . . . 80

BIOGRAPHICAL SKETCH . . . . . . . . ... .. 83

Abstract of Thesis Presented to the Graduate Council
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy




August 1982

Chairman: William M. Jones
Major Department: Chemistry

Protonation of (n5-cyclopentadienylirondicarbonyl) cyclooctatetraene

with strong acid produced the novel homoaromatic carbene complex n -

cyclooctatrien-l-ylium-n5-cyclopentadienylirondicarbonyl (FpHCOT ). Ex-

amination of the 1H nmr spectrum of this compound revealed a decrease in

the homoaromaticity of the homotropylium ligand when compared with homo-

tropylium itself, consistent with the expectation that significant di pi

backbonding interactions into the positively charged ligand by the organo-

iron occurs. Substitution of triaryl- or trialkyl-phosphine for a car-

bonyl on the cyclopentadienyliron in the carbene complex sequentially re-

duces the degree of aromatic delocalization in the homotropylium ligand,

providing clear evidence that significant increases in the backbonding

character of these complexes occurs when the electron density on iron

increases, as expected from our earlier work.

Furthermore, the three sets of proton coupling constants in the

homotropylium ligands reveal increased bond alternation as the other or-

ganic ligand is changed from CO to P(Ph)3 to P(Bu)3. This bond alterna-

tion was used to substantiate the relative measure of the aromatic ring

current the difference in proton chemical shift between the homocon-

jugate exo and endo protons (A6). When the As of the three homoaromatic

carbene complexes was compared with that of several other substituted

homotropyliums, an approximate measure of the T backbonding ability of

the cyclopentadienyliron group relative to normal organic functional

groups was obtained.

The thermal decomposition of FpHCOT appears to proceed through a

1,2-8 hydrogen shift mechanism. However, the complex has been isolated

as the hexafluorophosphate salt and could be manipulated if kept cold.

That these carbene complexes having B hydrogens are isolable at all was

postulated as being due to both the stabilizing effect of the homoaroma-

ticity, and the nearly orthogonal orientation of the B hydrogen bonds

and the carbene r system.

Additionally, the isodynamic interconversion processes of three cy-

clopentadienyliron substituted cyclooctatetraenes were studied by nmr.

The initial data appear to indicate that an unusual interaction between

the transition metal and the 4n i electron ring system may be present.


The general class of organometallic compounds known as carbene com-

plexes are thought of as the formal result of allowing an organic carbene

species to approach a ligand substituted transition metal in such a way

that the filled sp2 orbital and unfilled p orbital of the carbene inter-

act with appropriate empty and filled orbitals of the transition metal to

form a compound of the two species. Although no carbene complex has been

produced by this procedure, alternative methods have been developed which

have allowed the isolation and characterization of several of these


One of the most widely used synthetic procedures was developed by

Fisher and Maasbbl.3 Heteroatom stabilized carbene complexes were pro-

duced by organolithium attack on a carbonyl ligand followed by alkylation

of the anionic intermediate.

RLi /R (Me)30BF4

n-0 +
M(CO)n (CO)M _M --C


n(CO)n-M C (CO) M- C
SOMe n-1 OMe

The resulting neutral compound can be characterized as a neutral

metal carbonyl accepting electron density from the filled sp2 orbital

of the "carbene" to form a sigma bond. As a result of this bonding, the

now electron rich metal can release electrons in a d orbital with sym-

metry appropriate for "backbonding" into the unfilled p orbital on the

carbene carbon. Alternatively, the heteroatom substituent can compete

with the metal for bonding into this empty orbital. This or some other

form of additional r stabilization can substantially increase the stabil-

ity of carbene complexes. For example, the methylene carbene complex (1)

is known to have a transitory existence, but cannot be observed spectro-

scopically even at temperatures as low as -80C. However, phenyl


/ Fe Fe / Fe
CO --H CO -H or CO / C--H


1 2

substitution at the carbene carbon atom stabilizes the complex to such an

extent that the benzylidene complex (2) is isolable.4

Both the above methylene and benzylidene complexes were produced by

protonation of the sigma bonded metal a-methyl ether to remove the

methoxy group as methanol. The remaining positively charged carbon can

be stabilized as indicated. Removal of a good leaving group has become

a versatile method of producing cationic carbene complexes.

A variety of additional carbene complexes have been generated

through other methods, including two general classes of aromatically

stabilized carbene complexes.5'6

(CO)5r + C > ---- (CO)5Cr =

H 6
Fe Fe
CO 03- CO 3C+


The cationic cycloheptatrienylidene complex (3) was also formed by

removal of a negative leaving group, in this case a hydride, through use

of the hydride abstracting agent triphenylcarbenium ion.

A useful method of forming a cationic carbon site in carbonium ion

chemistry which has not apparently found application in metal carbene

chemistry has been protonation of an alkene. Such a procedure would gen-

erally produce an intermediate which would rapidly decompose by a 1,2

hydrogen shift to reform the alkene as a 7 complex with the metal.7


Fp L//7 H
S Fp= Cyclopentadienylirondicarbonyl

All of these carbene complexes can be represented as resonance hybrids
of three canonical forms

M- M M-

1+ 1


each of which makes different contributions to the overall structure in
the (several) individual types of carbene complexes. A qualitative in-
dication of the contribution by these resonance forms can be obtained
from the measurement of barriers to rotation about the appropriate
double bonds. For example, a barrier of 12.4 kcal/mol has been observed
for the carbene carbon-oxygen bond rotation in pentacarbonyl[(methoxy)
(methyl)carbene]chromium (0)8 (page 1, M=Cr), as well as a 9.1 and 10.4
kcal/mol barrier in Cp(CO)2Fe=CHC6H5+ (4) and Cp(CO)2Fe=CH(p-CH3C6H4)
(5), respectively, for the Caryl-Ccarbene bond.9


4^ a

&G = 9.1 kcal/mol

AG* = 10.4 kcal/mol


For CpFe(PPh2CH2CH2PPh2)=CH2+ (6) the barrier to rotation about the

metal-carbene bond of 10.4 kcal/mol was compared favorably10 with the

calculated electronic barrier.11




While these figures may not be strictly comparable, they do reflect the

fact that contributions by resonance forms B and C can be significant.

When X and Y in these resonance forms are the same and represent a

conjugated (4n +2)r electron ring system, the aromatically stabilized

carbene complexes (e.g. 3) result. Because of the aromatic delocaliza-

tion of the positive charge in the carbene ligand, contributions from

resonance structures having double bond character between the metal and

the aromatic ligand, representing metal dr pr backbonding, should be

substantially reduced.

M: M:

X-ray structures of CpFe(CO)2=C7H6+ (3) and CpFe(CO)2=benzoC7H4 the

aromatic tropylidene complexes produced by Allison and Jones, clearly

indicate a high degree of aromaticity and concurrent reduced backbonding

in these complexes. But when the iron-carbene bond length was compared

with two other model systems, only "some degree of metal-ligand multiple

bonding" was suggested.12

In an effort to better identify the contribution of metal-carbene

backbonding interactions in these aromatic complexes, rotational bar-

riers were obtained for the nonsymmetrically substituted iron carbene

complexes Cp(CO)PBu3Fe=C7H6+ (7) and Cp(CO)PBu3Fe=benzoC7H4+ (8).13

The rotational barriers observed, 9.6 and 10.4 kcal/mol respectively,

were unexpectedly comparable to the much more strongly a bonding species,

CpFe(DIPHOS)=CH2+ (6), which had been found to have a rotational barrier

of 10.4 kcal/mol.10 Because the X-ray data for compounds 3 and

Fp=benzoC7H4+ indicated weak backbonding, it seemed likely that "the

principle restriction to rotation [in 7 and 8] was steric in origin with

a minor electronic component superimposed."13

At the time that this last work was being done, characterization of

a new carbene complex was being completed, the spectral properties of

which were seen to have significant bearing on the question of the rela-

tive contribution of metal i backbonding in aromatic carbene complexes.

Rather than stabilizing the positive charge in the carbene ligand

by aromatic delocalization, this new complex was thought to achieve a

large measure of its stability through homoaromatic delocalization.

While this is a difference merely of kind rather than of function, a

wealth of information was believed to be available from this system when

compared with the cycloheptatrienylidene complex. In particular, since

the difference in chemical shift of the inner and outer proton of homo-

conjugate CH2 linkages is thought to be a definitive measure of the extent

of aromatic delocalization,14 and since this delocalization will be re-

duced by competitive delocalization of the positive charge through reso-

nance contributions due to metal backbonding, it was recognized that a


SM + ,M:

purely electronic measure of metal-carbene a bonding interaction could be

obtained from homoaromatic carbene complexes by the examination of the

difference in chemical shift of the homoconjugate protonsmentioned above.

A further point of interest is the fact that no other homoaromatic

carbene complexes have been reported in the literature.

This work will therefore describe the synthesis and characterization

of the first homoaromatic carbene complexes. Furthermore, a strong corre-

lation will be made between the i bonding ability of cyclopentadienyliron

groups and the + of normal organic functional groups.

q* +1

The Fpbenzocyclobutenylidene complex reported by Giering and Sanders15
is an unlikely candidate for homoaromatic delocalization because of the
required loss of aromaticity and increases in strain energy.


The synthesis of the first homoaromatic transition metal carbene

complex was accomplished by the synthetic route shown below.

0 Br Br



SFe Fe


9 10

Bromocyclooctatetraene was prepared as previously reported.16 Treatment

of the bromide with potassium cyclopentadienylirondicarbonyl7 produced

the (r5-cyclopentadienylirondicarbonyl) cyclooctatetraene (FpCOT) (9).

This reaction is unusual in that the Fp anion is normally used to

Except the dehydrobomination reagent, potassium t-butoxide, was dis-
solved in THF rather than added as the solid.


displace alkyl halides; however, it was noted that King had successfully

displaced fluoride from fluorobenzenes with Fp anion,8 and similar re-

action with BrCOT seemed feasible. The cyclooctatetraene sigma compleJ9

was formed via this reaction in higher yield and with more convenient

work up than our earlier method using cyclooctatetraenyllithium20 and Fp

iodide. The structural proof of the cyclooctatetraene sigma complex

rests on its well resolved IH nmr.spectrum and the observed conforma-

tional interconversion processes videe infra). Finally, the homoaromatic

carbene complex, n -cyclooctatrien-1-yliden-n -cyclopentadienylirondicar-

bonyl hexafluorophosphate (FpHCOTHFP) (10), was produced by protonation

of the FpCOT with strong acid and subsequent anion exchange using tri-

phenylcarbenium hexafluorophosphate, to yield a very thermally sensitive,

but air stable orange solid in 40% isolated yield from the sigma complex.

Because of the thermal instability of this carbene complex, the

structural proof relies heavily on the 1H nmr which is seen in Figure 1.

The single proton resonance of 8.9 ppm occurs at the characteristic low

field of protons adjacent to the carbene center6 and attests to the un-

symmetrical nature of the ring system in which the homoconjugate linkage

is also immediately adjacent to the carbene center.


Other possible structures would require two proton resonances at this

characteristic low field, which is not observed. Furthermore, protona-

tion of the FpCOT adjacent to the substitution is expected since the


-- (~

3 *

'- C

o u


3 C)

e n
E i


1 ^1- E

development of the charge in the transition state would best be stabil-

ized by the B substituent.


Fp ---- +Fp

The next four resonances occurring at 7.8, 7.5, and 7.3 ppm were

identified by irradiation studies as H5, H6, and H3 and 4 overlapping,

respectively. These resonances occur upfield of the corresponding

signals centered at 8.5 ppm in homotropyliuml4 itself videe infra) and

reflect both decreased positive charge density and reduction in the

aromatic deshielding in this carbene complex, as would be expected were

backbonding by the metal into the positively charged ring significant,

as will be discussed below.

5.6 1.3 5.1 0.7

58 Fp 6.5 H 8.4
5.8 8.9

7.5 +-I 7.3 8.4 8.6

7.8 7.3 8.6 8.3

The next resonance at 5.8 ppm is coupled only to H6 and the remaining

two split resonances, and so must correspond to H7 since no other proton

can be strongly coupled with more than two protons. The large singlet

resonance at 5.3 ppm is due to the cyclopentadienyl group associated

with the iron. The last two resonances at 5.6 and 1.3 ppm result from

H8 exo and H8 endo, respectively, and are only half the intensity of the

other single proton signals. This was caused by use of FSO3D as the

reagent when forming this sample, and results in the equal population of

both exo and endo sites with deuterium and hydrogen. This equal isotope

population could have been caused by exchange due to bridge flip isomeri-

zation or nonspecific protonation videe infra) and allows spin-spin

coupling of the homoconjugate bridge protons only with H7 (no geminal

coupling) resulting in the observed doublets. Triplets of correct area


Fp Fp


due to geminal and adjacent coupling are observed when protic acids are


The assignment of the resonances at 5.6 and 1.3 ppm to H8 exo and

H8 endo respectively rests with the observed cis and trans 3 bond

coupling constants compared with other homotropyliums.21'22'23

H 8.2

9.7 7.3


H 7.2


H' H
9.2 7.7


Furthermore, the

H8 endo can only

periphery of the

9.8 7.5


extreme difference in chemical shift between H8 exo and

be explained by the positioning of H8 endo within the

aromatic ring current and outside the periphery for H8

H8 endo H8 exo


In these positions the bridge protons are strongly influenced by the local

anisotropy of the aromatic ring current caused by the presence of magnet-
ic field B. This anisotropy powerfully shields H8 endo and deshields H8

exo, producing the observed chemical shifts 1.3 and 5.6 ppm respectively.

While the magnitude of the ring current that produces a change in

chemical shift, AS, between the exo and endo protons of 4.3 ppm must be

considerable, a valuable comparison can be made with non-metal substitut-

ed homotropyliums. It has been reported that the A6 of homotropylium

itself is 5.8 ppm, and is due to a ring current of the same order of

magnitude as that in benzene.14

The A6 of FpHCOT is substantially smaller than the Ad of homo-
tropylium and must represent a decrease in the extent of delocalization

or a significant distortion in the geometry. While the steric bulk of a

cyclopentadienyliron is considerably greater than many organic groups,

it will be shown videe infra) that steric changes in the organometal sys-

tem are not the dominant influence in the reduction of A6 and that this

change in A6 corresponds better with the backbonding ability of the cy-

clopentadienyliron substituent.

The decreased delocalization observed in FpHCOT+ can be thought of

as the result of backbonding by the Fp substituent into the homoaromatic

T system and consequent localization of the a electrons and positive

charge. Additional spectral evidence that significant iron carbene

carbon double bonding exists is found in the 13C nmr spectrum of this

Fp- = Fp--

compound (Figure 2). Large low field chemical shifts of the carbene car-

bon have been found in Fp carbene complexes.6 The resonance of the

II- S-0

= .0 .
u ar- 0


7 -J
C 0 C- c

S 0 -0
5 .--

41 Q) r_
u cu cu.

SI O w o

C -4 -
u >j ) U,-0

a (.
S- "
^ I- i"
v =1*r i
S. r 1
r 4- ) *CT
m n0
S ^ u c^ -- 1
: ^ ^ Q- (0 10 t/
2 ? i c c
a Ocn 1
S- t1 *- (3

carbene carbon at 269 ppm for FpHCOT is 147 ppm further downfield than

the comparable resonance at 122 ppm in homotropylium,24 and represents

a greater downfield shift than is observed in Fp+=cycloheptatrienylium,6

consistent with the expectation that a homoaromatic delocalization would

Fp 161

Fp+ 269 24

A = 147 ppm A = 81 ppm

be more readily disrupted by backbonding than a fully aromatic delocali-


The above evidence clearly supports the description of this material

as a homoaromatic carbene complex, a hitherto unknown compound having im-

portant ramifications in the descriptive chemistry of aromatic carbene

complexes. Two additional carbene complexes of cyclooctatrienylium will

be described,each having a ligand of different electronic and steric

characteristics, in an attempt to better characterize the overall struc-

tural and electronic properties of these homoaromatic complexes.

The three carbene complexes described in this work all have a com-

mon starting material in (n5-cyclopentadienylirondicarbonyl)cyclooctate-

traene, FpCOT. This sigma complex and its phosphinylated derivatives

have some interesting properties involving the conformational intercon-

version processes of cyclooctatetraene which will be discussed here.

A synthetic route from cyclooctatetraene (COT) producing reasonable

yields of FpCOT was described earlier. This substituted COT was found

to have an unusual property apparent from the 'H nmr in Figure 3. The

COT resonances are spread out over a range of nearly one ppm, a remark-

able change from the normal broadened singlet observed for all other

monosubstituted COT's. This is apparently an anisotropic effect due to

local variations in the applied magnetic field near the iron atom com-

bined with conjugative effects, because acyl complex 11, in which the

iron and COT are "insulated" from one another by the carbonyl, does not

0 0

KFp + C Fp


show the expansion of the COT resonances, but simply exhibits the normal

broadened COT singlet (Figure 4).

In effect, this sigma bonded complex, FpCOT, contains an internal

shift reagent. This expansion of the COT resonances dramatically eases

structural identification and the observation of the well-known COT in-

terconversion kinetics. Unlike previous studies of COT where examina-

tion of 13C satellites at low temperatures25 and full line shape26

analysis was required to determine proton coupling constants and chemical

shifts, this information can simply be measured from the spectra of the

sigma complex (Figure 5).












,. )L

4 1

a 0


0 *

C- C

U 2 Q.
,n D.

= C
S.-- S.-





01 ~
a l




S- E
E 0-

Ln n

0 me
*I -


0 9-0

Ln 0
0 E -0
S 0 (U
C 4


C Lj

t1 t~,

5* ii
4Sr Cr


J (.)




Uc C=
4 -' ,
i- V5



CE .

5--1 (- 5


Fp 3.4 Hz

HH \ 10.9 Hz
11.1 H
2.8 Hz 3.2 Hz

The close match between the reported coupling constants of 11.4 and
3.87 for COT,25 and the respective couplings in FpCOT implies that

little steric distortion occurs even though Fp is by far the largest re-

ported COT substituent.

FpCOT, like COT, undergoes isodynamic ring interconversion processes

(Figure 7). These processes were studied by diastereomer exchangel5 and

line shape analysis26 for COT and several monosubstituted derivatives and

were found to have free energy of activation barriers ranging from 12.5

to 14.8 kcal/mol for the Ring Inversion (RI) processes, and 14.9 to 17.4

kcal/mol barriers for Bond Shift (BS) interconversions.27 The measurement

of this Bond Shift activation barrier, in all reported cases in the lit-

erature, is performed by observation of the kinetic exchange of signals

due to R2 and R8. It is necessary to use complicated line shape analy-

sis26 to identify the R2 and R8 resonances when monosubstituted COT's

(R1 f H) are being investigated, although multisubstituted COT's can be

more easily examined by observing exchange of the substituent resonances.

This skew coupling constant has a reported range of ca. 2.5 to 3.87


0 ,




1 m
/ 4-

'^ C.o
) = "" 0 e.

-R R

However, R2 = H2 and R8 = H8 resonances of monosubstituted FpCOT

are easily identified (H2 at 5.68 ppm and H8 at 6.16 ppm in Figure 5)

and the sample may simply be warmed to coalesce these resonances (Figures

8 and 9) to identify-AGBS = 17.9 kcal/mol.

This same procedure was used to measure the Bond Shift activation

barriers for two other substituted sigma complexes. Both of these new

compounds, (n5-cyclopentadienylironcarbonyltri-n-butylphosphine) cyclo-

octatetraene (FppBuCOT) 12, and (n5-cyclopentadienylironcarbonyltri-

phenylphosphine) cyclooctatetraene (FppCCOT) 13, were made in high yield

via photolysis of FpCOT in presence of tri-n-butylphosphine or triphenyl-

phosphine respectively.

The simple coalescence formula28 has been applied to determine rate
constants at the coalescence temperature. Although this equation is
strictly applicable to the exchange of single lines of equal population,
negligible errors will result when applied to coupled lines if J is much
less than 6v as applies here (J/Sv ca. 0.2). A precision of 0.5 kcal/mol
results when the possible range of temperatures at coalescence is ca.

4> C

u -
A) C
LL >

E4- 40


5- H- E
S4- a
o *

a Q r

=e C *-




Ln a
o 0

4-> -P-

o .0

o- o

S. -

Q- CI-




R = Bu




hP 3 / \COT
3 CO C PR3




It will be observed that the major spectral difference between FpCOT and

these compounds (Figure 10 and Figure 11) other than the phosphine

ligand signals, is the double multiplicity of the cyclopentadienyl (Cp)

and COT resonances. This is due to the diastereomerism inherent in these

molecules. It is well known that monosubstituted COT's are chiral and it

should be evident that these organoiron moieties are "pseudotetrahedral"

and are thus chiral when substituted with a phosphine ligand. These

chiral metals are optically stable in the temperature range of interest29

but this is not true of the COT ligand. Both the Ring Inversion and











N C,




L -C

o .a



L 3 Cs (

L, : r i



Bond Shift processes exchange configurations,30 and the rapid exchange
of diastereomers results. This exchange can be observed as the

S Fe


COFe /


averaging of the nmr Cp resonances due to the diastereomer pairs in each
of these phosphinylated sigma complexes. This behavior is shown in
Figure 12.


I i


Figure 12. 1H nmr of exchange between
diastereomeric cyclopenta-
dienyls in FppBuCOT. The
fine splitting seen in the
low temperature spectrum is
due to the 1.1 Hz 31p-1H








Because AGBSt is usually substantially greater than AGRI and thus

the rate constant kBS very much smaller than kRI, observation of race-

mization of COT or exchange of diastereomers is generally attributed to

RI processes exclusively.26 (For an exception see reference 30.) This

was assumed when calculating28 the AGRI for FppBuCOT and Fpp0COT as

17.0 and 17.3 kcal/mol respectively.

As discussed previously, the observation of exchange in the COT re-

sonances is a phenomenon due exclusively to Bond Shift processes and is

entirely separate from the above consideration. In fact the activation

energies observed for the coalescence of the COT resonances in these

Table 1. Approximate Activation Barriers












AGt in kcal/mol

*Potentially available from the averaging
in the 13C nmr (Figure 6).
AGt RI 0.2; AGt BS 0.5 videe supra)

of diastereotopic CO resonances

phosphinylated sigma complexes are the only additional values necessary

for a complete solution of equations30 describing the activation barriers

AGRIt and AGBS Unfortunately, these results were obtained with a pre-

cision that could adversely affect the overall results (due to an instru-

mental difficulty) and so this experiment must be redone more carefully.

Nonetheless, it is apparent that AAG the difference in activation

barriers for the Bond Shift and Ring Inversion processes (AGBS AGRI)

is smaller than, by possibly as much as one half, the AAGt for other

reported monosubstituted COT's.27

Table 2. Ring Inversion and Bond Shift Activation
Substituted Cyclooctatetraenes
















Barriers for Various







AGt not corrected for small variations due to differing temperatures.

If these results are borne out by further experiment, the unusually small

AAGt seen for iron substituted COT's must be explained.

One possibility is an increase in electron density in the planar

transition state caused by backbonding from iron disturbing the antiaro-

matic delocalization characteristic of the high energy Bond Shift transi-

tion state, and reducing the total energy of the Bond Shift pathway.



This is feasible since the occurrence of metal i backbonding into aryl

systems should be more disfavored than metal T-antiaromatic system in-

teractions, yet is known to exist.31'32

Alternately, steric interactions are known to increase in going to

the planar transition state and can cause reduction in the AAG.30

While the steric demands of the iron substituent are not high, steric

interactions do occur and can be observed using "fast" spectroscopic

techniques like IR.33 Still, it is unlikely that steric interactions in

this system can be of the same order of magnitude as in 1,2,3-trimethyl-

COT, which is the least crowded COT reported to depress AAGt values to

below 2 kcal/mol.30





Clearly additional work needs to be performed on these systems be-

fore final conclusions may be drawn, but it should be noted that an ex-

planation of the small observed AAGt should be accessible. This is be-

cause the FppBu substituent is smaller than the Fpp0 substituent34 and

also is more electron donating relative to Fpp,; if steric interactions

are more significant in reducing AAG' the larger group, Fpp,, should

have decreased AAGt, while if electronic effects dominate, the more

electron donating group, FppBu, should have decreased AAGt. The latter

effect seems to be indicated from the present data.

This result would be interesting because it would be a rare, if not

exclusive, example of the effect of backbonding by an organometallic sub-

stituent into an antiaromatic ring system. A significant comparison

could then be made between the above effect and its counterpart in the

aromatic carbene complexes.

As discussed earlier, protonation of the FpCOT sigma complex pro-

duced a new homoaromatic carbene complex. Similarly, protonation of

FppCOT leads to n -cyclooctatrien-1-ylidene-n -cyclopentadienyliron-

carbonyltriphenylphosphine (FppgHCOT ) (14) which can be isolated as its

hexafluorophosphate salt. Although this compound is considerably more

Fe. 2) HFP


thermally stable than the parent homoaromatic carbene complex, FpHCOT+,

it too is thermally labile and will decompose upon standing at RT for

several hours. Therefore, once again the structural proof relies on the

nmr spectra (Figures 13 and 14). As can be seen in the proton nmr, the

most downfield signal at 8.5 ppm represents one hydrogen adjacent to the

carbene center and identifies the structure as being similar to the

parent FpHCOT The large multiplets at 7.5 and 7.4 ppm are due to the


triphenylphosphine (P03) ligand, and the next four resonances at 7.1,

6.8, 6.6, and 6.5 ppm are H5, H6, H4, and H3 respectively as identified

by decoupling. The quartet resonance at 5.4 ppm next to the solvent sig-

nal is H7. The Cp resonance occurs at 4.9 ppm. The last two resonances

represent the two geminal protons of the homoconjugate CH2 linkage,

identified as H8 exo at 4.8 ppm and H8 endo at 1.7 ppm by their coupling

7.2 8.2 8.9
9.8 7.2 10.0 7.3 8.9 7.7
-H -Fp -- Fpp




+ 0)




L ai

L *
0 ro-


+ Co
- CJ

4-. O
UX ..


4- QC

4-, 1-






constants, separated in chemical shift once again by the anisotropy of a

substantial ring current.

However, it is expected that this ring current would be reduced re-

lative to the parent carbene, FpHCOT because backbonding by Fppo into

the homoaromatic ring should be more favorable than backbonding by Fp.10

This is because substitution of a phosphine ligand in place of a carbonyl

results in greater electron density on iron. This will allow increased

Fppg backbonding and increased localization of electrons in the cyclo-

octatrienylidene I system. The reduction in the ring current explains

Fe + Fe
P03 P03

the decrease in the difference in chemical shift of H8 exo and H8 endo,

A6, to a value of 3.11 ppm, down from 4.30 ppm observed in FpHCOT+ and

5.86 ppm in homotropylium itself.

That the diminuation of A6 is an electronic effect rather than a

simple steric influence is supported by the extreme low field shift of

the carbene carbon resonance in the 13C nmr (Figure 14). The signal

(doubled by phosphorous coupling) occurs at 311.4 ppm, nearly 200 ppm

downfield from the C-1 resonance in homotropylium, and is further down-

field than that observed for the same carbon in FpHCOT This indicates

greater backbonding contributions,3 consistent with the observed

Fpp F 311;: Fp H

Fpp Fp=4 H-

changes in the proton nmr A6. Furthermore, the difference in shift of

the homotropylium ligand C-1 carbon between Fpp HCOT+ and FpHCOT+ is 42

ppm, similar to the analogous difference of 37 ppm6,13 observed in the

cyclophetatrienylidene series and reflects similar changes in backbond-

ing due exclusively to ligand substitution.

Another property of this carbene complex gives additional evidence

that greater backbonding occurs than that seen in FpHCOT It was ob-

served that exchange broadening and shifting of the signal due to H8 endo

occurred in the proton nmr for temperatures greater than 00C (Figure 15).

This was originally construed to indicate exchange with excess acid used

to produce the nmr solutions of the carbene. However, disappearance of

the signal was not observed when using deuterated acid; rather, the in-

tegrated signal intensity was seen to remain at one half proton. More-

over, exchange of this signal occurred when the hexafluorophosphate salt

Fpp0HCOT HFP was dissolved in solvent containing no acid. Therefore no

acid exchange process was present.



o a 1


L um '
C40 0 10

a*)- CL
O r- r-

L, S O

V 0 =
L VI -


CO N 01 MW E
CD 1- 0)

C (D o
No Stu E

S ? r- L. L

5 IL

It is known that homotropylium undergoes an exchange process in

which the homoconjugate CH2 unit flips from a position above the approxi-

mately planar235 seven membered ring to a position below it. The



activation barrier measured by Winstein for this process was 22.3

kcal/mol.36 Substitution of C-1 on homotropylium with a methoxy group

reduces the activation barrier to 19.6 kcal/mol.23 Brookhart interpreted

this reduction as being due to the greater substituent stabilization of

the positive charge on the sp2 rehybridized C-1 of the transition state
15 than the substituent stabilization of the charge on the more sp


R &9R
15 16

hybridized C-I of the ground state 16.23

With this in mind, a re-examination of the kinetic behavior of

Fpp HCOT+ indicated that the signal due to H8 exo may have been obscured

by the Cp resonance in the 100 MHz nmr. Protonation of FppOCOT in d6
benzene shifted the Cp resonance (probably due to Cp-benzene stacking

interactions) to reveal the now relatively unobscured H8 exo resonance

which showed temperature dependent exchange broadening. This same phe-

nomenon was seen in the 300 MHz nmr (Figure 15). The exclusive exchange

of H8 endo and exo signal is taken to indicate that the bridge flip pro-

cess occurs much more rapidly in Fppg substituted homotropylium than in

normal homotropyliums since exchange broadening in 1-hydroxyhomotropylium

is not seen even to 800C.22 Accurate activation barriers have not been

obtained since thermal decomposition occurs rapidly above 60C although

a barrier of ca. 14 kcal/mol was estimated from line shape changes.

However, it was seen that this exchange process in FppgHCOT occurred

more rapidly than in FpHCOT because no exchange broadening was observed

when FpHCOT was rapidly heated to decomposition at 50C. (Unfortunate-

ly, unlike other homotropyliums,233637 no exo-endo specificity is seen

when deuteration of FpCOT is carried out even at-1000C and therefore the

kinetics of signal appearance could not be observed.) This last obser-

vation of faster exo-endo exchange in FppgHCOT than in FpHCOT is con-

sistent with Brookhart's interpretation that the activation barrier for

bridge flip interconversion is reduced when more powerful electron

dontaing substituents are present at C-i, the more powerfully donating

substituent in this case being Fpp .

A caveat is appropriate at this point in that the straightforward

interpretation of the H8 exo- H8 endo broadening presented here is likely

too simplistic to account for more recent spectral observations of this

phenomenon. High field nmr spectra which resolve the H8 exo signal show

that it exchanges and shifts toward low field rather than towards the H8

endo signal at higher field. Speculation as to the nature of this pro-

cess or of the possible superimposition of an additional process upon the

normal bridge flip exchange is currently in progress.

A somewhat more electron releasing substituent would be n5-cyclo-

pentadienylironcarbonyltri-n-butylphosphine, FppBu. However, because

the cone angle of occupied space in ligand PBu3 is only 130 degrees as

opposed to 145 degrees for P03,34 this substituent should be sterically

less demanding than Fppo. If steric factors play a significant role in

the structural and electronic properties of these organoiron substituted

homotropyliums, a reversal in the spectroscopic trends as seen for

FpHCOT and FppgHCOT should be apparent in the spectrum of n -cyclo-


FpPBuHCOT+ (17) (Figure 16).

When FppBuCOT is protonated to produce this final new homoaromatic

carbene complex, the general trends are preserved. The difference in

shift of the CH2 protons, A6, is 2.98 ppm, a value slightly less than

the A6 of 3.11 ppm observed for FppHCOT in accord with the slightly

greater electron releasing ability of the FppBu substituent. The chemi-

cal shift of the carbene carbon is 315.7 ppm, again indicative of

slightly better backbonding in this complex relative to Fpp0HCOT+ (the

C-1 of which appears at 311.4 ppm). In fact, all the spectral details

of these two phosphinylated carbene complexes are rather similar, except

for one difference. The chemical shift of the two homoconjugate protons

are both shifted about three quarters of a ppm (0.68 ppm for H8 exo and

0.81 ppm for H8 endo) downfield from their counterparts in Fpp0HCOT.

While no assumptions have been made concerning the linearity of the

absolute magnitude of the chemical shifts due to the H8 protons as a

function of ring current (an assumption which has been specifically con-

traindicted 36), it is believed that a direct and linear relationship

holds for the comparison of AS and the magnitude of the ring current when










Do r

w 1





u u






relatively constant geometries are assumed.14'16 While the expected and

observed results of this work are consistent with the latter statement,

it is somewhat bothersome that a slight deviation in the expected pat-

tern of convergence of the H8 shifts exists for FppBuHCOT This


'" H H8 exo
H8 endo
3 :
6 "-- FppBu
1 I I -EP

1 2 3 4 5 6

deviation can be seen above in the convergence of H exo-H endo shifts

with increasing electron donation capability of the 1-substituent in

the homotropylium ligand.

Whatever the source of this deviation, it is apparent that it

results in a slight variation in the geometry of the molecule. This can

be seen by the examination of the complete set of bridge coupling con-

stants for these three systems and the comparison of these data with

other substituted homotropyliums vide infra.

One of the most often cited indications of homotropylium structure

is the two bond proton proton coupling constant for H8 exo H8
21 22,23,38
endo.21222338 When originally formulated Rosenberg, Mahler and
Pettit were undecided about the electronic structure of protonated

cyclooctatetraene (HCOT ). Subsequent work led them to strongly support

the homoaromatic structure.38 However, Deno preferred a description of

the molecule as the bicyclic species.40 Winstein pointed out that the

bicyclic form was unlikely in that the expected proton coupling constants

for a cyclopropylcarbinyl system were not consistent with the observed

couplings in HCOT+41 vide infra.

A B8

JA,B= ca. 4.7 Hz

JA,C= ca. 4.5 Hz

JBC = ca. 8 Hz

As can be seen below, the geminal and three bond cis and trans

coupling constants of the organoiron substituted homotropyliums are

quite similar to those observed in HCOT+ and other substituted homotro-


H 8.2 H

9.7 73

H8~ H

9.2 7.7

H 7.2H

9.8 7.2


9.8 7.5


H, -H

Clearly these carbene complexes are not distorted toward a closed

cyclopropane type structure. Nor do the coupling constants reveal any

significant departure from a relatively constant geometry, even though

FppBuHCOT couplings reflect a small variation in the trend. What is
exemplified in the above is the marked similarity between the homotro-

pylium carbenes and the homotropyliums substituted with electron

It should be pointed out that the figures for Fpp HCOT were far more
difficult to determine because of overlap of H7 and H8 signals in the
proton nmr, and probably have a larger error than the other carbene data.

donating groups. These similarities give strong support that the

changes observed above are primarily geometrical changes that result

from electronic interactions. That small geometrical changes do occur,

resulting from electronic interactions, can be seen through examination

of the 13C-11 coupling constants at C8. In cyclopropylcarbinyl this

13C-1H coupling is 180 Hz or more.42 In homotropylium, due to the modi-

fied a type interactions between C-1 and C-7, the larger C1-CH2-C7 bond

angle is expected to cause reduction in the s character in the CH bonds,

leading to decreased coupling interactions between the 13C and 1H nuclei.

The observed hydrogen-bridge carbon coupling in homotropylium is 159


0 R
J = 180 Hz 1J 8,H 159 Hz C8,H= 130- 136 Hz

Hz,21 and the expected reduction in 1,7 bonding in FpHCOT and
+ *
FppgHCOT produces the even smaller couplings, ca. 131 Hz and 136 Hz


* +
The somewhat low value for FpHCOT is probably an inaccuracy caused by
the method used to obtain it. The actual value measured was the 13C-
deuterium coupling constant, which was then multiplied by the ratio of H
and 2H magnetogyric ratios to calculate the 1H-13C coupling.

This reductioninl,7bonding due to backbonding by the iron substitu-

ent should also be accompanied by increased localization of the T system.

This effect can be seen in the coupling constants of the protons about

the periphery of the nearly planar seven membered ring portion of these

systems (Figure 18).

These values must be compared with the only other complete set of

coupling constants available,21 those from homotropylium itself. The

differences between these two sets of values arise from the unsymmetrical

backbonding substitution of the homotropylium framework and manifest

themselves as an alternation in the magnitude of the coupling constants

due to apparent i localization and consequent alternation of the double

and single bond character in the ring system. Prior to the recent X-ray

structural verification35 and the impressive theoretical calculations by

Haddon,43 the coupling constant information for homotropylium was the

best evidence that homotropylium was comprised of a distinctly puckered

but symmetrical seven membered ring portion (7MR).21 A modified, but

similar geometry is though to exist videe infra) in the homoaromatic

carbene complexes.

The nonsymmetrical substitution of homotropylium, along with sequen-

tially increasing backbonding by the cyclopentadienyliron series, Fp,

Fpp0 and FppBu, should lead to sequential increases in the localization

of the i electron density and thus the alternation of the coupling con-

stants. The full set of proton coupling constants for these molecules

(Figure 18) are consistent with this and are quite accurate, as can be

seen in the spectral simultions based on the evaluated couplings in

Figures 19, 20 and 21. Interestingly, the asymmetry of the line shapes

in FpHCOT+ (Figure 19) is related to the symmetry of a portion of its


8.6 .4
10.1 ( hiZ)i
10.1 7.4



9.1 N -
11.4 9.0


11.5, /
8.9J Fpp0

11.6 8.5

7,8 endo = 10.0

J =8.9
7,8 endo 9

7,8 exo 7.7


8.9 PPBu

11.5 8.5

7,8 endo 8.1

7,8 exo 77

Figure 18. Proton-proton coupling constants for homo-
tropylium and the three homoaromatic carbene
complexes. All values reported in Hertz.

7,8 endo =9.8
J exo = 7.2
7,8 exo

7,8 exo


= 7.3

= 0.9





L -
CO 0 -a


L i-

- LL


Q -


4 -
4- C0

C 41





:, -' C

C +D
U 4-

E >

t -o



7MR, which causes an unusually large long range coupling of 0.9 Hz be-

tween H2 and H5. Significant through space interactions such as this

usually occur only when the bonds of the interacting nuclei are nearly

colinear. The long range coupling (together with the extensive Tr

H Fp


delocalization) helps to verify the approximate planarity of the 7MR in

this Fp carbene complex.

The more strongly backbonding substituents, Fpp, and FppBu, could

cause an increased distortion of the 7MR from planarity as increases in

the alternating bond character allow torsional changes to occur. That

this is an electronic effect is shown by the correlation of backbonding

strengths (but not steric considerations) and coupling constant alterna-

tion. The difference between adjacent couplings is presented in Table 3.

3 2

4 6
5 6

Table 3. 1H Three Bond Coupling Constants for Monosubstituted Homotro-
pyliums, and Differences in Adjacent Couplings.

2, 3 J3, 4 4, 5 J5, 6 6,7

HCOT+ 8.6 10.1 10.1 8.6 7.4
1.5 0 1.5 1.2

FpHCOT+ 9.7 9.1 11.4 6.9 9.0
0.6 2.3 4.5 2.1

FppOHCOT+ 11.5 8.9 11.6 6.4 8.5
2.6 2.7 5.3 2.1

FppBuHCOT+ 11.7 8.9 11.5 5.7 8.5
2.8 2.6 5.8 2.8

What is to be noted here is that the increase in dr pi backbonding (which

restricts the delocalization of the 7MR ir system) as R becomes H, Fp,

Fppo and FppBu causes the difference in the adjacent coupling constants

to generally increase--as would be expected were the difference in the

adjacent bond characters to increase.

This pattern authenticates the proposal that the geometry of homo-

tropylium carbene ligands is more responsive to the electronic behavior

of the cyclopentadienyliron than to the possible steric interactions.

Because of this, the observation that the variation in the difference in

chemical shifts (A6) of the bridge protons corresponds primarily to the

iT electronic interaction capabilities of the organometallic substituent

should stand on a firmer basis.

With this in mind, it is pertinent to note once again that both the

A6 and bridge coupling constants fall in the range of respective values

arising from a variety of 1- substituted HCOT+'s. Thus it seems possi-

ble that a direct comparison with normal organic functional groups may

reasonably be made. There does not appear to be any significant indica-

tion in the previous data or discussion that would argue against such a


Table 4. Comparison Between Various R Substituted Homotropyliums.

Ha Hb


H c

Ha H

H ,Hc




R groups H21 Me38

Fp Fppo FppBu

OH22 OMe22

gem 7.2 8.0 8.2 8.9 8.3 10.8 10.5

Jtrans 9.8 10.0 10.0 8.9 8.1 9.2 9.8

Jcis 7.2 7.5 7.3 7.7 7.7 7.7 7.5

A6 5.8 5.0 4.3 3.1 3.0 3.1 3.1

The thrust of much of this work's discussion has been the valida-

tion of the relationship between the magnitude of the homoaromaticity

as measured by A, and the r donation capability of the cyclopentadienyliron

groups. The analogous measure of the T donating ability of organic func-
+ 44
tional groups is the a .

When the a+ of the substituents of the reported 1-substituted

homotropyliums is plotted against the A6 of that compound a relatively

straight line is produced (Figure 22). Locating the A6 value of the

three carbene complexes FpHCOT FppHCOT and FppBuHCOT on this line

produces a values of -0.43, -0.80, and -0.84 respectively. These num-

bers should at best be considered approximations, and it would be wise

to think of a phosphinylated cyclopentadienylironcarbonyl group (Fpp) as

having about the same electron donating ability as a hydroxy or methoxy

group, and of a cyclopentadienylirondicarbonyl group (Fp) as a substan-

tially weaker donor. Nonetheless, this is the first sensitive indica-

tion of organoiron T donating strength directly comparable to normal

organic groups. Other comparative methods have not been sensitive
enough to separate carbonyl and phosphine substitution effects,4546

-.2 M ..--Me
4 .. _ -. 6 OMe+ +
-8 FpPu 0 PP
1 .4 ,

-1 .8 .- 0
-2 I
0 1 2 3 4 5 6
Figure 22. Least squares plot of A5 vs. o for
R substituted Homotropyliums. a
of 0- estimated from value of a
for NMe2 44,47,48,49

much less the backbonding effects of alkyl versus aryl phosphine sub-

stitution as observed in this work.

This comparison fairly sharply delineates the a donor capability

of Fp and Fpp in the homotropylium system. Certainly some variation in

this parameter would be expected with other carbene ligands having dif-

ferent electronic demands. Nonetheless, an approximate indication of

the relative backbonding or i donating ability of these organoiron

groups has a clear advantage over the activation energy of rotational

barriers as a predictive descriptor in the chemistry of these cationic

carbene complexes. This is especially true in the 6w electron aromatic

series, the members of which have notable steric contributions to their

rotational barriers.13

For the sake of comparison, an attempt was made to measure the bar-

riers to rotation in the three homoaromatic complexes as well, but this

data could not be collected. In the case of FpHCOT any barrier to ro-

tation was expected to be low through analogy with the proposed small

barrier in Fp+=C7H6 (3).13 No changes in the 1H nmr of FpHCOT were

seen between temperatures of -1000C to -100C, above which decomposition

was seen to occur rapidly. (Highly acidic conditions were seen to alle-

viate this thermal sensitivity somewhat, so that the rapid heating to

500C was accomplished in 90% trifluoroacetic acid without spectral changes

other than final decomposition.) Combined with the observation of a

single set of diastereotopic carbonyl resonances in the 13C nmr (Figure

2), the spectral data point to rapid (nmr time scale) rotation about the

iron-carbene bond.

diastereotopic CO/ "-chiral

On the other hand, the large phosphine group in the FppHCOT 's

could be expected to interact even more strongly with the rotating car-

bene ligand than was seen in FppC7H6+ (7) in which a 9.6 kcal/mol elec-

tronic and steric composite barrier to rotation was observed,3 because

the greater backbonding videe supra) in the homoaromatic complexes would

not only lead to closer proximity of the ligands, and thus increase

steric interactions, but would also increase the electronic contribution

to the rotational barrier. However, no spectral changes were seen from

-1000C to 500C other than the previously mentioned exchange broadening

of H8 exo and H8 endo. In view of diastereomerism inherent in these

O Fe Fe


FppHCOT complexes, it is possible that a considerable difference in the

energy of the two diastereomers could prevent the observation of an ex-

change between signals of greatly different intensity in the proton nmr.

This diastereomerism may be the cause of difficulty in obtaining

crystalline salts of the Fpp complexes. In both FppBuHCOT HFP (17) and

FppgHCOT HFP (14) only amorphous solids could be collected after careful

attempts at recrystallization. Since the non-diastereomeric FpHCOT HFP

(10) crystalline solid was ultimately too thermally sensitive for X-ray

analysis, the symmetrical bis(1,2-diphenylphosphino)ethane (DIPHOS) sub-

stituted carbene complex was sought. It was hoped that this compound,

n -cyclooctatrien-1-yliden-n -cyclopentadienyliron[bis(1,2-diphenyl-

phosphino)ethane] hexafluorophosphate (CpFe(DIPHOS)HCOT HFP) (18), would

be more thermally stable than the other HCOT+ carbenes, would crystallize




for X-ray analysis, possess adequate symmetry for rotational barrier de-

tection and provide a final point for comparison of + and 66. However

the starting material n5-cyclopentadienyliron[bis(diphenylphosphino)-

ethane] cyclooctatetraene (19), could not be synthesized, as discussed




Addition of DIPHOS to FpCOT by photolysis occurred with rapid evo-

lution of carbon monoxide, but the mixture of products did not contain

substituted cyclooctatetraene, nor did addition of strong acid to a so-

lution of this material produce any carbene complex signals in the nmr.

Addition of cyclooctatetraenyllithium (LiCOT)20 to cyclopentadienyl-

iron(DIPHOS)chloride was not attempted since the addition of cyclohepta-

trienyllithium to the chloride did not yield a desired product.50

Reaction of LiCOT with [CpFe(DIPHOS)]2N2(HFP)251 produced a very

small yield of a mixture possibly containing the product 19, but this

was not followed to conclusion because of the extremely low yields.

This line of research was abandoned in order that other pertinent

questions might be addressed. For example, the thermal decomposition of

FpHCOT HFP (10) was shown to produce a COT complex of Fp This probably

precedes via a 1,2-8 hydrogen shift7 from the homoconjugate CH2 to pro-

duce the olefin complex (n5-cyclopentadienylirondicarbonyl)-n2-cyclo-

octatetraene (Fp -COT) (20). A possible52 mechanism for this process is
indicated below.






The structure of this product was established by the release of COT
(as identified by H nmr) from a solution of the thermally decomposed
carbene complex via nucleophillic displacement of the COT from Fp with
sodium iodide.53 Also observed in the products was Fp iodide.



+ FpI

This reaction was verified by grinding the thermally decomposed
FpHCOT HFP (10) with KC1 prior to introduction in the mass spectrometer.
A reaction analogous to that seen in solution apparently occurs in the
solid state, since COTP was identified (high resolution in accord with
m/e calculated for COT) as well as trace signals attributable to the
modestly volatile FpCl and its fragmentation products.

This decomposition is exactly what is expected of a nonheteroatom

stabilized organometallic carbene complex having B hydrogens present.7

On the other hand, the exhibited stability of these homoaromatic carbene

complexes is more analogous to that of heteroatom stabilized carbene

OMe OMe /OMe

(CO) Cr--C t (CO)Cr =C\ r- (CO)5Cr-C
CH 21 CH3 H

complexes such as 21. Neither the homoaromatic nor heteroatom stabilized

carbene complexes undergo facile 1,2-hydrogen transfer reactions, proba-

bly because the carbene centers are part of the conjugated i systems.

However, pentacarbonyl[(methoxy)(methyl)carbene]chromium (0) 21, is some-

what acidic,54 and thereby indicates the availability of its Tr hydrogens

for 1,2-shift decompositions. This points out another possible stabil-

izing factor in these homotropylium carbenes: the nearly orthogonal or-

ientation of the homoconjugate CH2 bonds to the metal carbene conjugat-

ed T system. Without appropriate orbital orientation, 1,2-hydrogen

shifts cannot occur.

This would imply that the pathway to decomposition is the bridge

flip intermediate, where neither stabilizing effect mentioned above is

as effective.


A problem here is the observation that the FppHCOT 's are more

thermally stable than FpHCOT yet with Fpp substitution, this bridge

flip intermediate should be more accessible videe supra), therefore

leading to more rapid decomposition. It is possible, however, that

greater backbonding by Fpp would reduce the charge density on C-1, thus

inhibiting 1,2-hydrogen shifts relative to Fp substitution.

Nonetheless, it is apparent that the ground state homoaromatic

carbene complex is a modestly stable organometallic species having B hy-

drogens present. This is sufficiently rare enough to warrant note,55

but it is clear that the geometrical alteration upon protonation to form

these complexes is quite unique, so that this method of forming carbene

complexes should not be regarded as having general utility.

In conclusion, the synthesis and characterization of the first

three homoaromatic carbene complexes are described in this work and a

strong correlation has been made with the r backbonding ability of cyclo-

pentadienylirondicarbonyl (Fp) and cyclopentadienylironcarbonyltrialkyl

(or aryl)phosphine (Fpp), and the + of normal organic functional groups.

Additionally, three novel organoiron sigma bonded complexes of

cyclooctatetraene (COT) were developed for the above work which dramati-

cally display the known isodynamic conformational processes of COT, and

which may reveal a hitherto undescribed organometallic interaction with

a 4n n electron orbital system.



The melting points were obtained on a Thomas Hoover melting point

apparatus and are uncorrected. Nuclear magnetic resonance spectra were

obtained on either a Jeol FX-100 or Nicolet NT-300 spectrometer, and are

reported in ppm relative to TMS or the deuterated solvent resonance.

Coupling constants for the nmr spectra were either measured directly if

the line was a simple doublet or simulated using the Nicolet 1180 ITRCAL

program. Infrared data were obtained on a Perkin-Elmer 137 spectropho-

tometer. Combusion analyses were performed by Atlantic Microlab Inc.,

Atlanta, Georgia. Mass spectra were obtained on an AEI MS 30 spectro-


All nmr solvents were degassed by bubbling nitrogen through the

cold solvent for ten minutes and subsequently stored in a Vacuum Atmo-

sphere Inc. recirculating glove box under oxygen-free conditions. All

other solvents were distilled. All solvent and reagent solutions were

swept free of 02 by bubbling N2 through the solution for at least ten

minutes when dealing with air sensitive compounds. THF was distilled

from benzophenone ketyl using Na/K alloy. Methylene chloride was dis-

tilled from P205.

The alumina used was Fisher certified neutral alumina, Brockman

Activity I, to which 3% w/w water was added. After the addition of

water, the alumina was allowed to stand at least 12 hours before being

purged several times with nitrogen immediately prior to use. All reac-

tions were performed under a nitrogen atmosphere and Schlenk type appa-

ratus was used when appropriate.

Cyclopentadienylirondicarbonyl Iodide (Fpl)

This material was used as supplied from Alfa Products.

Tri-n-butylphosphine (PBu3)

This material was used as supplied by Aldrich Chemicals after de-

gassing with N2.

Triphenylphosphine (P03)

This material was recrystallized from 95% ethanol. It was obtained

from Aldrich Chemicals.

Bis(l,2-diphenylphosphino)ethane (DIPHOS)

This material was recrystallized from acetone. It was obtained

from Alfa Products.

Trifluoroacetic Acid (TFA)

This material was distilled and degassed prior to use. d -TFA was

made by hydrolysis of acetic anhydride with D20.

Triphenylcarbenium Hexafluorophosphate (03C HFP)

This material was used as purchased from Aldrich Chemicals.

Fluorosulfonic Acid (FSO3H)

This material was distilled and degassed with nitrogen bubbling

before use. FSO3D was used as purchased from Aldrich.

Potassium Cyclopentadienylirondicarbonyl

This material was made according to the method of Gladysz et a.17

Bromocyclooctatetraene (BrCOT)

To a dry 1000 mL 3 necked round bottomed flask equipped withmechan-

ical stirring, N2 bubbler and a 300 mL addition funnel, and containing

47.2 g (0.45 mol) of freshly distilled cyclooctatetraene (COT) dissolved

in 500 mL dry CH2C12 at -780C was added dropwise 25.0 mL (77.5 g, 0.48

mol)Br2in25 mLdry CH2C12.

After stirring for 15 minutes, 75 g (0.67 mol) potassium t-butoxide

dissolved in 250 mL dry THF was added portionwise to the dibromide

solution over the course of 6 hours, maintaining the temperature between

-60 and -780C. The mixture was stirred overnight at low temperature and

then, after warming to room temperature, poured over 500 mL crushed ice,

swirled gently and placed in a separatory funnel. The organic layer was

separated, and the aqueous layer and emulsion mixed with 50 mL diatoma-

ceous earth, suction filtered and extracted with 3x50 mL CH2Cl2. The

combined organic layers were washed with water, dried over MgSO4 and

flash evaporated at room temperature.

The crude BrCOT was mixed with an equal portion of pentane, filter-

ed through alumina and flash evaporated to obtain a dark yellow liquid

which was carefully distilled between 40 and 450C at 0.5 torr to collect

70 g BrCOT as a yellow oil in 85% yield. The IR and nmr spectral pro-

perties are in accord with those reported in the literature. 20

Cyclooctatetraene Carboxylic Acid (COT-CO2H)

To a stirred solution of 6.4 g (34.6 mmol) BrCOT in 50 mL dry

ethyl ether and 4.0 g clean Mg turnings was added ca. 2 mL of a 1:1 solu-

tion of ethane dibromide in ether. The solution was warmed to initiate

the reaction and then placed in an ice bath with the slow addition of

the remainder of the 1:1 dibromide-ether solution (total ethane dibro-

mide 6.5 g, 34.6 mmol) such that ethylene continued to be evolved with-

out interruption. The solution was strongly stirred for about 3 hours

and then rapidly siphoned over crushed, dry, solid CO2. After warming

to RT, the mixture was extracted with 3x100 mL H20. The aqueous layer

was then acidified to pH 3 to form a cloudy yellow suspension of COT-

CO2H. This was extracted with 3x50 mL pentane, dried over MgSO4 and

rotovapped to an oil which crystallizes to form yellow plates after

standing for several days to produce 3.25 g COT-CO2H in 64% yield.

COT-CO2H: mp 66-69C; 1H nmr (CDCl3)6 5.9 (s, COT), 10.3 (br s, 1H).

Cyclooctatetraene Acid Chloride (COT-COC1)

Cyclooctatetraene carboxylic acid (3.07 g, 20.7 mmol) was placed in

a 50 mL round bottomed flask equipped with magnetic stirring, reflux

condenser and heating mantle. To this was added 6.8 g (4.4 mL, XS)

oxalyl chloride in 10 mL benzene portionwise with much bubbling. The

solution was allowed to stir until CO evolution ceased and then was

gently refluxed for 2 hours. The excess benzene and oxalyl chloride

was removed by flash evaporation, and another 20x2 mL benzene added

and removed to separate the product from residual oxalyl chloride. The

brown oil was then distilled at 520-56C at 0.05 torr to yield 3.25 g

COT-COC1 in 93% yield. COT-COC1: IR (neat) 3010, 2400, 1750, 1625,

1250 cm1.

(n5-Cyclopentadienylirondicarbonyl)cyclooctatetraene Carbonyl (11)

To a stirred solution of 1.3 g (6.2 mmol) KFp in 30 mL dry THF at

-78C was added dropwise 1.1 g (6.6 mmol) cyclooctatetraene acid chlo-

ride in 15 mL dry THF. After completion of the addition, the stirred

solution was allowed to slowly warm to room temperature over the course

of 2 hours. The reaction mixture was then coated onto 10 mL of silica

gel by flash evaporation and chromatographed on a 6 by 1 inch silica

gel column using benzene as eluent. After the brown Fp dimer band was

eluted, the yellow band of acyl complex was carried off the column by

adding up to 50% CHC13 to the benzene eluent. The product, 0.62 g of

11, was collected as a yellow-orange crystalline air stable solid in

36% yield after evaporation. 11: mp 106-110C with decomposition; IR

(CHCI3) 2000, 1600 cm-1; 1H nmr (CDC13)6 4.9 (s, Cp), 5.9 (s, COT).

Photolysis of 11

No products other than highly insoluble solids were obtained after

photolysis of hexane or MeC12 solutions of 11 using either pyrex or

quartz filtered 550 W Hanovia Hg lamps.

(n5-Cyclopentadienylirondicarbonyl)cyclooctatetraene (FpCOT) (9)

To a rapidly stirred solution of 1.0 mL (1.42 g, 7.8 mmol) BrCOT
in 250 mL dry, 02 free THF was added 3.5 g (16 mmol) KFp in THF at room

temperature. The addition of the KFp solution was performed at high

dilution (to reduce Fp dimer formation) by a modified, nonsiphoning

Soxelet extraction of the modestly soluble KFp by refluxing the THF

under reduced pressure (90 120 torr) while maintaining the solution

temperature at room temperature with a heating mantle (BrCOT is thermal-

ly labile). After no further KFp was extracted, the darkened reaction

mixture was vented with nitrogen and stirred overnight. The crude mix-

ture was then coated onto 10 mL of Grade II Fisher neutral alumina by

flash evaporation and chromatographed on a 1 by 4 inch degassed, Grade

II Fisher neutral alumina column using degassed hexane as eluent. A

pale yellow BrCOT band preceded the intense yellow FpCOT band which was

collected under nitrogen to produce 0.94 g FpCOT in 43% yield. The

yield varied between 20 and 43% depending on the dilution of the Fp

anion addition. This yellow, air-sensitive oil should be stored re-

frigerated in solution (do not use CHC13). FpCOT: Anal. calcd. for

C15H13FeO: C, 64.31; H, 4.32. Found: C, 64.07; H, 4.40; IR (film)
2960, 1990, 1925, 1560, 1400, 1005, 909, 827, 802, 714 cm-; 1H nmr

(300 MHz, CD2C12)5 4.81 (s, Cp), 5.22 (dd, H7, J7,8 =11.1 Hz, J6,7=

3.4 Hz), 5.51 (dd, H5, J5,6= 10.9 Hz, J4,5=3.2 Hz), 5.68 (fine d, H2,

2,3 =2.8 Hz), 5.75 (dd, H6), 5.77 to 5.85 (m, H3 and H4), 6.16 (d, H8);
1C nmr (d6-acetone)6 87.2 (Cp), 119.3, 129.2, 132.6 (2C), 136.7, 139.3,

147.7, 151.7 (C1), 217.2 (CO), 217.7 (CO); mass spectrum m/e, 280.01984

(calcd. 280.01850).

An alternative synthesis produces FpCOT in lower yield. To a cold

(-780C) solution of LiCOT, made by the method of Cope and Burg20 from

2.42 g (13.2 mmol) BrCOT, was added 4.50 g (13.2 mmol) Fpl in 20 mL dry,

02 free THF dropwise with stirring. After stirring for 2 hours at

-780C, the solution was allowed to warm to room temperature and stirred

for an additional I hour. The dark mixture was adsorbed onto 10 mL

degassed Grade II neutral alumina and chromatographed as above using a

12 x1 inch column. The product, 0.61 g FpCOT, was collected in 16%


(n5-Cyclopentadienylironcarbonyltri- n-butylphosphine)cyclooctatetraene
(FppBuCOT) (12)
To a solution of 0.23 g (0.82 mmol) FpCOT in 50 mL dry, 02 free THF

in a tall, narrow Schlenk tube was added 0.30 mL (0.24 g, 1.2 mmol, 1.5

fold XS) tri-n-butylphosphine. Nitrogen was bubbled briefly through the

solution to sweep out residual 02 and the solution was then irradiated

through Pyrex under N2 at RT (H20 cooled jacket) 6 inches from a 550 W

Hanovia Hg lamp. The reaction progress was monitored by taking 0.2 mL

aliquots and evaporating to dryness, redissolving in CHCI3 and observing

the 2000 cm-1 region for disappearance of the two Fp absorptions and

appearance of the single FppBu absorption at 1925 cm-1. Photolysis ap-

peared to be complete after 3 hours but was continued 1 additional hour.

The product, 0.35 g (0.77 mmol) FppBuCOT as a yellow-orange air-sensi-

tive oil, was collected in 94% yield after chromatographing the reaction

This is essentially the same as the procedure reported by Cooke et al19

mixture as described above for FpCOT. This material should be stored
in the same manner as the parent FpCOT. FppBuCOT: IR (CHC13) 2995,
1925 cm1; 1H nmr (d6-acetone)6 0.9 to 1.9 (m, butyl), 4.4 and 4.5

(d's, Cp, diastereomers with JHP= 1.1 Hz), 4.9 (m, H7), 5.3 (m, H5),
5.6 (m, H2, H6, H3, H4), 6.3 (m, H8); 13C nmr (d6-acetone)6 24 to 32
(butyl), 83.6 (d, Cp, diastereomers), 115.7 (d, diastereomers), 127.4
(d, diastereomers), 132.0 (s), 133.3 (d, diastereomers), 137.0 (2C, d
below 00C), 149.9 (d, diastereomers), 167.1 (dd, C1,diastereomers),
221.9 (dd, CO).
Alternatively, FppBuCOT can be produced without isolating FpCOT.
Addition of 2 fold XS (based on an assumed 40% yield of FpCOT) of tri-
n-butylphosphine to the crude rxn mixture of FpCOT in THF followed by
overnight photolysis as above with stirring produced greater than 90%
yields of FppBuCOT after workup.

(n -Cyclopentadienylironcarbonyltriphenylphosphine)cyclooctatetraene
(FppOCOT) (13)
FppCOT was prepared in greater than 80% yield from FpCOT by using
a 1.5 fold XS of triphenylphosphine in the primary synthesis described
above, however photolysis occurred more slowly. To a solution of 0.85

g (3.0 mmol) FpCOT in 100 mL dry, 02 free THF was added 1.44 g (5.5 mmol)
triphenylphosphine. After overnight photolysis under N2 using the pre-
viously described photolysis set up, the reaction mixture was coated
onto 15 mL Grade II neutral alumina by flash evaporation and placed on a
1 by 4 inch column of degassed, Grade II neutral Fisher alumina in hex-
ane. After eluting the XS P03 and unreacted FpCOT with hexane, an
orange band was collected under N2 by eluting successively with 5% and

10% MeC12 (or ether) in hexane. The product, 1.3 g (2.5 mmol, 82%)

FppCOT as an air stable orange glass, remained after removal of the
solvent. This mixture of diastereomers could not be recrystalized even

after repeated attempts. Fpp COT: Anal. calcd. for C32H27FeOP: C,

74.72; H, 5.29. Found: C, 74.49; H, 5.35. IR (CHC13) 2995, 1920 cm-1
H nmr (300 MHz; CD2C12)6 4.45 and 4.49 (d's, Cp, diastereomers with

JHP=1.1 Hz), 4.91 (dd, H7, J7,8=11.11 Hz, J6,7 =3.22 Hz), 4.95 (dd,
H7', J7',8 =11.02 Hz, J6',7 = 3.22 Hz), 5.30 to 5.84 (complex, H2, H5,

H6, H4, H3), 6.10 (dd, H8), 6.29 (dd, H8'), 7.37(br s, O's); 13C nmr

(CD2C12)6 85.4 (d, Cp), 116.6 (d), 130 to 140 (0 and COT), 149.5 (s),

164.4 (dd, C1 of COT), 222.3 (dd, CO). Mass spectrum m/e, 486 (M-CO),

383, 262 (100%), 224,121, 56.

traene (CpFe(DIPHOS)COT) (19)

This compound could not be produced by the methods discussed below.
Photolysis of 100 mg FpCOT with 1.2 equivalents DIPHOS in d6-benzene was

performed using all quartz glassware and a 550 W Hanovia Hg lamp. After

5 minutes, CO evolution was observed but the nmr spectrum of the solu-

tion appeared unchanged. After 45 minutes of photolysis, several Cp re-
sonances had replaced the original Cp signal at 4.5 ppm. Chromatography

yielded only mixtures of unidentified products. Similar results were
obtained when the above photolysis was carried out in THF using a pyrex
filtered lamp. An alternative method also did not yield the desired

product. A suspension of the highly insoluble [CpFe(DIPHOS)]2N2(HFP)2
salt produced by the method of Sellman and KleinschmidtS1 (0.237 g,

0.175 mmol in 50 mL THF) was added to 0.5 mmol LiCOT20 in THF at -780C

and stirred overnight at low temperature. No color change was observed

until the solution was warmed to RT, after which the evaporate was

coated onto 5 mL degassed Grade II neutral alumina. Chromatography pro-

duced hydrocarbon products along with a small quantity of possible pro-

duct 19 visible as a small set of signals at 6.5 ppm (COT) and 4.5 ppm

(Cp) in the nmr. Although the low yield of products was probably due to

the insolubility of the nitrogen complex, no other appropriate solvents

were found.

n -Cyclooctatrien-I-ylium-n5-cyclopentadienylirondicarbonyl Hexafluoro-
phosphate (FpHCOT HFP) (10)

Excess anhydrous HC1 carried by N2 was bubbled through a cold

(-400C), magnetically stirred solution of 0.31 g (1.1 mmol) FpCOT in 25

mL degassed CH2C12 for ca. 15 minutes; the bright yellow solution imme-

diately turned deep red due to the presence of the homoaromatic carbene

complex. A two fold excess of degassed fluorosulfonic or trifluoroace-

tic acid in CH2CI2 could be used in place of the HC1. To the deep red

FpHCOT solution was added 0.43 g (1.1 mmol) triphenylcarbenium hexa-

fluorophosphate in 10 mL CH2C12 (anmonium hexafluorophosphate was not

soluble) and the FpHCOT PF6 salt precipitated by slow addition of an

equal volume of cold ethyl ether. The resulting microcrystalline orange

needles were collected by filtration under N2 on a glass frit surrounded

by a dry ice isopropanol cup. This thermally sensitive solid (stable

below -100C in air) was washed by the addition of 3 x2 mL of cold ethyl

ether and stored in the freezer (-300C). A yield of 0.19 g (40%) FpHCOT

was isolated from the FpCOT sigma complex. However, low temperature

protonation of FpCOT in CD2 C2 instantly generated nmr solutions of the

carbene complex quantitatively. These solutions must be rigorously 02
free. FpHCOT HFP: MP upon rapid heating, orange solid turns dark
brown at about 700C, melts at about 800C, and then turns black with ef-
fervescence at 1000-105C; IR (KBr) 2002, 1970, 1440, 1400, 1300, 1275,
1070, 980, 840 cm1; 1H nmr (300 MHz, CD2C12, -200C)6 1.27 (t, H8 endo,

8 endo, 8 exo 8.2 Hz, 7,8 endo =10.0 Hz), 5.26 (s, Cp), 5.57 (t, H8
exo J7,8 exo = 7.3 Hz), 5.78 (t, H7, J6,7 =9.0 Hz), 7.34 and 7.35 (m,
H4 and H3, J3,4=9.1 Hz), 7.47 (t, H6, J5,6= 6.9 Hz), 7.83 (m, H5,
J4,5= 11.4 Hz), 8.86 (d, H2, J2,3= 9.7 Hz, J2,5=0.9 Hz); 13C nmr
(CD2C12, -200C) 62.3 (C8), 89.8 (Cp), 133.2, 133.7, 134.3 (C4, C7, C6),
139.7 (C3), 143.2 (C5), 169.0 (C2), 210.4, 211.5 (CO's), 269.0 (Cl).

n -Cyclooctatrienyl-l-ylium-n -cyclopentadienylironcarbonyltri -n-
butylphosphine Hexafluorophosphate (FppBuHCOT HFP) (17)
This compound was produced from FppBuCOT in the same manner as des-
cribed above for the Fp carbene complex. The initially yellow orange
solution immediately became intense burgundy colored upon addition of
acid. The dark purple hexafluorophosphate salt is substantially more
thermally stable than the parent, but is not crystalline and is subject
to air oxidation. FppBuHCOT HFP: IR (KBr) 2970, 1960, 1485, 1465,1425
1080, 835 cm-1; 1H nmr (300 MHz, CD2Cl2, -200C)6 0.9 to 2.0 (m, Butyl),
2.48 (t, H8 endo, J endo,8exo=8.3 Hz, J7,8 endo= 8.1 Hz), 4.97 (d,
Cp, JHP= 1.2 Hz), 5.48 (m, H8 exo and H7, J7,8 exo = 7.7 Hz), 6.45 (t,
H3, J3,4 = 8.9 Hz), 6.62 (t, H4, J4,5 = 11.5), 6.73 (t, H6, J6,7 = 8.7
Hz), 7.04 (dd, H5, J5,6 = 5.7 Hz), 8.48 (d, H2, J2,3 = 11.7 Hz); 13C
nmr (CD2Cl2, -20C) 13.6 to 29.9 (n-Butyl), 62.7 (C8), 90.3 (Cp), 123.2,
130.1, 134.3, 135.4, 137.4 (C3 to C4), 161.5 (C2), 217.1 (d, CO, JCP =
28.1 Hz), 315.7 (d, C1, JCP = 22.0 Hz).

phosphine Hexafluorophosphate (Fpp0HCOT HFP) (14)

This deep purple amorphous salt was produced from Fpp0COT in the
same manner as described earlier for the Fp carbene complex except that
a two fold XS of TFA was used in place of anhydrous HC1. The thermal
stability of this compound is the highest of these three homoaromatic
carbene complexes. Brief exposures to as high as 500C in solution have
been tolerated with no decomposition. After vacuum drying the salt ap-
pears to be air stable indefinitely when kept cold (-10C); FppHCOT
HFP: MP upon rapid heating, dark purple solid turns ash colored at ca.
1000C, then darkens at 1500C without melting; IR (KBr) 2995, 1975, 1490,
1465, 1430, 1095, 845 cm1 ; H nmr (300 MHz, CD2C12, -200C)6 1.67 (t, H8
endo, J8 endo, 8 exo = 8.9 Hz, J7,8 endo = 8.9 Hz), 4.79 (t, H8 exo,

J7,8 exo = 7.7 Hz), 4.87 (d, Cp, JHP = 1.2 Hz), 5.42 (q, H7, J6,7 = 8.5
Hz), 6.51 (t, H3, J3,4 = 8.9 Hz), 6.66 (t, H4, J4,5 = 11.6 Hz), 6.78
(t, H6), 7.07 (dd, H5, J5,6 = 6.4 Hz), 7.37 to 7.77 (m, O's), 8.51 (d,
H2, J2,3 = 11.5 Hz); 13C nmr (CD2C12/TFA, -20C)6 61.7 (C8), 90.8 (Cp),
124 to 138 (Ring C's and O's), 161.5 (C2), 216.4 (d, CO, JCP = 29.3 Hz),
311.4 (d, Cl, JCP = 22.0 Hz).


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Marc Dudley Radcliffe was born in Schnectady, New York, in February

1953. After spending his early childhood on the coasts of New England,

he and his parents moved to Titusville, Florida. There he watched the

dawn of the space age and became interested in science. He attended

college at Miami University in Oxford, Ohio, Worcester Polytechnic In-

stitute in Worcester, Massachusetts, and finally at New College in

Sarasota, Florida, before finding employment in the semiconductor in-

dustry, where he participated in the development of the early digital

watch technology.

He returned to college at the University of Florida in 1975 and sub-

sequently received the Summer Undergraduate Fellowship in Chemistry. He

began his graduate work there in 1977 with Dr. William M. Jones, received

a supplemental graduate fellowship during his studies there, and has re-

cently accepted a postdoctoral position with Dr. Kurt Mislow at Princeton


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 chairman n
Professor of Chemikry

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.

Merle A. Battiste
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. Dolbier, Jr. /
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.

Eric V. Dose
Assistant Professor of Chemistry

I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of
Doctor of Philosophy.

Raymond J. Be geron
Associate Professor of Medicinal

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 Council, and was accepted as partial fulfillment of the
requirements for the degree of Doctor of Philosophy.

August 1982

Dean for Graduate Studies andResearch

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