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Ferrocene
255
FERROCENE ANNUAL
SURVEY
COVERING
BERNARD W. ROCKETT Department
and GEORGE MARR
of Physical
Wolverhampton,
THE YEAR 1983"
Sciences,
The Polytechnic
WV1 1LY (Great Britain)
CONTENTS 1.
Reviews
255
2. Structural
determinations
Theoretical
3. 4. 5. 6.
256
studies
Spectroscopic
and physico-chemical
Electrochemistry Preparations
10. Ferrocene
studies
and photosensitive
267
electrodes
272
of ferrocene
7. Reactions of ferrocene 8. Ferrocenium salts and mixed-valence 9. Ferrocenyl
259 259
carbenium
273 274
salts
277
ions
278
chemistry
(i) Derivatives (ii) General
containing
(metalloids)
ferrocenophanes
12. Ferrocene-containing
and annelated
ferrocenes
polymers
catalysts
307
stabilizers
(iii) Ferrocene
in analysis
(v) Biochemical
309
and photosensitizers
(ii) Ferrocene (iv) Combustion
296 309
of ferrocene
(i) Ferrocene
278 288
chemistry
11. Biferrocenes,
13. Applications
other metals
311
and improvers
312 313
control and biological
314
applications
14. References
317
1. REVIEWS Kauffman discovery
and aromatic stabilized
Cd
l
has recorded
of ferrocene character
+ Annual
Survey
Chem.,257
Referencesp.317
[l].
carbocations
The chemistry
the events
The chemistry
has been the subject
of chelate
covering
(1983) 209
that led to the
and the con'firmation of its structure
complexes
of ferrocenyl of a brief review
containing
organo-
the year 1982 see J. Organometal.
256
metallic
ligands with arene
has been surveyed
by Rybinskaya
organometallic
derivatives
2. STRUCTURAL
DETERMINATIONS
X-ray analysis ferrocene through clinic
was carried
temperature
of workers
face-centred
of 164K.
consisted
by X-ray diffraction The crystal
of ferrocene
and lattice
and molecular
Vinylferrocene
of molecular
The same group energy
structure
(2,l) has been determined
[7].
cooled
from room
structure
calculations
crystallography
crystal
When the tri-
[5].
the disordered
of the
by X-ray
has been attacked
(3-iodopentane-2,4-dionato)cobalt(III)
[4].
phase of
of a mixture
at room temperature dicyanovinylferrocene
The
triclinic
and 21 symmetry
investigated [6].
[3].
by cooling a crystal
its structure
groups
have been reviewed
out at 130K on a single
phase was obtained
packings,
and Krivykh
of ferrocene
of the metastable
the transition
temperature
and cyclopentadienyl
in the presence
by trisof
COMe
(W2
CMe=C
Fe
Fe
6
6 0
0
2.2
.2.1
triphenylphosphine ferrocenyl
and palladium(I1)
dihydrofurans
and 2.3) were mechanism
by which
structure
of the helical
X-ray
analysis. the two
they were
by X-ray
The compounds
crystallography
formed was discussed
ferrocene
This structure -cyclopentadienyl
7
to form the two isomeric
(2.2 and 2.3).
characterized
where
2.3
(2.2
and the
[8].
The
(2.4) has been determined
represents
by
the first ferrocene
rings are linked by unbroken
257
2.4 conjugation [y]. The crystal and molecular structure of benzyldiphenylferrocenylphosphonium chloride has been determined by X-ray The results indicated that it was possible for the analysis. filled hag molecular orbital of the ferrocenyl group to overlap with an empty 3d orbital of phosphorus. The implications of this overlap on the rates and stereochemistry of the Wittig reactions of (carbomethoxymethylene)diphenylferrocenyl- and (carbomethoxymethylene)diferrocenylphenyl-phosphorane with The structure of the benzaldehyde were considered [lo]. ferrocenylphosphine-rhodium complex (2.5; R = CMe3) has been determined by X-ray analysis. The rhodium atom was shown to be in a distorted square planar environment. The behaviour of the complexes (2.5, R = CMe3, Ph) as homogeneous catalysts in the hydrogenation of CH2=CRC02H, where R = NHCOCH , CH2CO2H, and PhCH=CRC02H, where R = NHCOCH3, Me, was investigzted [ll]. The crystal structure of the ferrocenyl quaternary ammonium salt c (7-CgH5)Fe(C5H4CHZNMe3)];1B10H10 has been determined by X-ray analysis [12]. The crystal and molecular structure of (ferrocenylmethyl)(l-cyclopentadienyl)dicarbonyliron has been determined by X-ray methods [13]. The crystal and molecular structure of the ferrocene (v-cyclopentadienyl)iron complex (2.6) and of three related complexes have been determined by X-ray crystallography [14]. Several methyl-substituted bis(7-pentadienyl)iron complexes, including the dimethyl derivative (2.7) have been prepared and
FLeferencesp.317
+ I6
258
L
Fe
7
“‘0;;
0
characterized molecular
as red air-stable
structure
crystallography.
eclipsed
ligand
a little greater properties
El51
conformation
The molecule
were similar
Fe Fe
2.7
adopted
with metal-carbon
l
301
and
(Z,7) has been determined
than those in ferrocene.
of the complexes
The crystal
compounds.
of one complex
by X-ray
2.6
a gauche-
bond distances
Physico-chemical to those of ferrocene
259
3.
THEORETICAL STUDIES
The effect of substituent groups and of ligand replacement on the frontier orbitals in ferrocene has been examined. Replacement of a cyclopentadienyl ligand by arene caused major changes in the el (antibonding) interaction which was decreased and in the back-bonding e2 (bondin&) interaction which was increased. The introduction of methyl substituents caused a minor increase in the el interaction and a minor decrease in the e2 interaction, The introduction of acetyl A force field study groups caused the opposite effect [16]. of ring orientation in ferrocene and ruthenocene has been Minima in the intermolecular strain energy carried out. corresponded to the observed conformations only if the relative orientation in all the neighbouring molecules was assumed to The bonding change with that of the reference molecule [17]. and reactivity of phosphaferrocene (3.1) and diphosphaferrocene have been studied by nonparametrized MO calculations. The ligands were shown to form Z-bonds with the metal 2 orbitals and the calculated electrondensity distribution in phosphaferrocene (3.1) was in accordance with the observed distribution. Charge control was important in determining the regioselective character of electrophilic substitution in phosphaferrocenes. Lone pair electrons associated with phosphorus were localized on that atom but did not confer nucleophilic properties on phosphorus since the lone pair was not in a frontier MO [~_a]. INDO-(crystal orbital)calculations have been used to obtain the energy band structure and density of electronic states in polyferrocenylene [lg]. 4.
SPECTROSCOPIC AND PHYSICO-CHEMICAL STUDIES
Intercalation compounds of ferrocene, lithium and pyridine derivatives in the layered transition metal oxyhalides MOX, where X = Cl, Br, M = V, Cr; X = Cl, M = Fe have been prepared and characterized by X-ray diffraction, voltamtnetric, Solutions of monosub'H NMR and Moessbauer methods [20]. stituted ferrocenes and biferrocene in freon mixtures have been The monocations produced subjected to y-irradiation at 78’~. from biferrocene and phenylferrocenes showed an absorption band that was assigned to electron transfer from ferrocenyl or phenyl
Referencesp.317
260
to the iron atom [21], ferrocene
tracer has been studied
The temperature probability splitting energies
Butylrubber
dependence
of resonance
and chemical
3d metallocenes determined
of the Moessbauer
parameters,
band widening,
shift, were determined unstable
negative
[22].
The of the
(4.1; M = V, Cr, Mn, Fe, Co, Ni) have been
by electron
scattering
assignment
quadrupole
ion states
transmission
spectroscopy.
(4.1; M = Fe, Co, Ni) calculations
complexes multiple
by \6-resonance spectroscopy.
absorption,
of the low-lying,
57Fe-enriched
containing
employing
XW method with stabilization
of the observed
metal 3d, 4elg orbital
states
to electron
or cyclopentadienylZ*
Q
Q-
6
6
the
permitted
capture
the
into the
orbitals
R
0
For the
[23].
CR1=NNHCOR2
0
F‘e
M
0
Fe
0
4.3
4.2
4.1
Open-shell, ferrocene, mission
vanadocene
metallocenes
The spectra
spectroscopy.
of multiple
scattering
and chromocene,
have been studied X&
and closed-shell,
by electron
were interpreted
calculations
[24].
copy has been used to investigate
the electronic zirconocene,
ferrocene.
The binding
were significantly groups
into a metallocene
reduction
energies
altered
The mass spectra
effects
hafnocene
of and
of the inner shell electrons
thus the introduction was equivalent
of the metallocene
by the use
ESCA spectros-
methylsubstitution
in titanocene,
trans-
of ten methyl
to a one-electron
[25].
of the substituted
R = COCH3, CH3, CHO, C02H, CH20H,
ferrocenes
COPh, CH2N(CH3)2]
t4.2; have been
261
reinvestigated making intensive use of the metastable ions. The observed primary fragmentations of the molecular ions were different in some respects from those previously suggested [26]. Acetyl- and benzoyl-ruthenocene and l,l'-diacetylruthenocene have been studied by mass spectrometry. The high metal-ligand bond strengths led to extensive fragmentation of the ligands by comparison with ferrocene [27]. The mass spectra of eight ferrocenyl aroylhydrazones (4.3; R1 = H, Me; R2 = Ph, substituted Ph, pyridyl) have been measured and interpreted in terms of skeletal and hydrogen rearrangements and bond cleavages The gas phase reactions of Fe+, Co+ and Ni+ with cyclic [28]. hydrocarbons have been investigated by Fourier transform mass spectrometry. The intermediate [Fe(C5H6)]+ cation combined readily with cyclopentane and underwent multiple dehydrogenations to give the ferrocenium cation [(C5H,-)2Fe]+[29]. Zagorevskii and co-workers have reported a correlation between mass spectra data and -endo-exo-stereoisomerism in the rhodium complexes R = ferrocenyl, methyl and 4.5; exo-isomers shown) (4.4; [301
l
&j----Hb&m__ OH
R \ 0
H
9 ’ ‘_.*’
Me& 4.4
e 4.5
Photoionization efficiency curves have been recorded for ferrocene vapour between 1900.and 590 8. The parent ion had an appearance potential of 6.747 eV and the [(7-C5H5)2Fe]+ fragments [(v-C5H5)Fe]+ and Fe+ appeared at 13.162 and 13.506 Ferrocene and bis(q-arene)chromium eV respectively [31]. complexes have been ionized on a tungsten oxide surface.
Fleferencesp.317
Ferrocene
formed a molecular
observed.
The ion current
approximately
ion but no fragment increased
1150K the coefficient
ions were
with temperature
of surface
and at
ionization
was
8 x 1O-3 [32]. A Moessbauer been carried liquid
crystals
dissolved
study of anisotropic
over the temperature
range
and reappeared
Au- and 57Fe-Moessbauer ferrocenyl-gold presence
complex
Au(PPh3)2
of cyano biphenyls
80-300K.
spectra
(4.6).
effect
was changed
have been recorded [34].
BF -
4
with the
A series
-
+e
[33].
for the
Q-Q
+
Fe
or
The data was consistent
in the complex
has
in
and terphenyls
The Moessbauer
as the temperature
of Au(I) and Fe(I1)
6
diffusion
dissolved
of i-methoxybenzylidene-~-butylaniline
in a eutectic mixture
c@appeared
molecular
out with l,l'-diacetylferrocene
of
+
Fe
0
4.6
l,l'-diacetylferrocene
complexes
SnCl 4, FeC13 and TiC14
has been studied
of the Lewis acids AlC13, by Moessbauer
All the complexes exhibited a lowering COPY. splitting relative to the uncomplexed ligand. in quadrupole chemistry polymers
sp'litting were discussed
of the complexes
[35].
based on vinylferrocene
Moessbauer copolymer
spectroscopy. exhibited
fraction
between
motional
narrowing.
anharmonic
A Moessbauer
The decreases properties
have been investigated
of
by
Acrylonitrile-vinylferrocene
an anomalous The results motion
of quadrupole
in terms of the stereo-
The dynamic
decrease
80 and 130K accompanied
hindered
spectros-
of the recoil-free by line broadening
were interpreted
of the ferrocenyl
and electrochemical
and
in terms of
group [36].
study has been carried
out on
263
(4.7; X = Cl, Br, I). The Moessbauer (4.7; X = Br, I) indicated average valence states for the iron atoms but the cation (4.7; X = Cl) the haloferrocenes spectra
showed
of the cations
a trapped
difference
was
valence
state
for the iron atoms.
found in the half-wave
potentials
No
of these
[371.
molecules
The 57 Fe Moessbauer
spectra
and &cyclodextrin
derivative-x-
-od-cyclodextrin clathrate which
collapsed
terms of reorientation of Gcyclodextrin
of ferrocene have been recorded
of the formylferrocene-
consisted
of a doublet
at low temp-
on heating
to a singlet
of reduced
This variation
intensity.
clathrates
the spectrum
For example,
at 78-320K. eratures
of a series
in the spectrum
was interpreted
of the formylferrocene
as the temperature
in
in the cavity
increased
Moessbauer
[38].
spectroscopy
has been used to study oxidation
interaction
irreversible
phase transitions
of ferrocenium
ion-iron
oxychloride
between
intercalates
of the type [(7-C5H5)2Fe]+
with 57 Fe labelled
[(6-7FeOCl)]the unstable
dynamic
ferrocenes.
e-e[Fe2+
At low temperatures
Eq. 4.1 and Eq. 4.2 in the
equilibria,
Ferrocene#[Ferrocenium]+ Fe3+OCf+
layers
and
+ e-
para OCl]-
Eq. 4.1 or [Fe2+ antiferro
OCl]-
Eq. 4.2 guest and host layers respectively phase
transitions
[39].
The 57 Fe chemical sensitive
indicator
shown by high anisotropy, anistropy determined
shift in ferrocenes
of ring tilting
field shifts
the electric of ferrocene
bonding
quadrupole
moment
resulted
axes.
in directions
It was indicated
in transfer
constants
was found
chemical
have been
have been used to show that
of electronic
rings
[41].
parallel
that metalcharge
from
The 13C and
(4.8;
of the benzylideneferrocenophanediones
carbon
being
and the magnetic
R1 = H, Cl, Br, NMe2, OMe, Me, N02, CN, R2 = H; R2 = Cl, Br) have been recorded and interpreted. of the carbonyl
tilting
polarization
in cyclohexane
were more polarizable
the metal to the cyclopentadienyl 'H NMR spectra
with increased
and ruthenocene
to the ligand-metal-ligand
has been used as a
The effective
[40].
The results
at 25'C.
these metallocenes -1igand
gave rise to irreversible
R1 = H, A correlation
shift with the Hammett
for both z- and E-CO groups
[42].
Electron
264
Fe
4.8
4.9
P-cocH=c Fe
Fe
ti
0 4.11
4.10
density
distributions
(4.9, 4.10, 4.11; using
in the phenyl-ring
effects
of substituents
and
13C N?iR spectroscopy.
on electron
The 57 Fe NMR spectra with natural
of
was
28 mono- and di-substituted 57Fe have been recorded using
reference.
on the high-frequency
shielding
effect of substituents
was shown
to be important
carried
distributions
abundance
as an internal
were mainly
A complete
density
The
[43].
ferrocenes ferrocene
ferrocenes
X = H, ;-CHO, 2 -0Me) have been measured
cyclic voltammetry
discussed
substituted
molecular
was discussed
in determining
dynamics
out in E-xylene
The resonances
observed
side of the reference.
study
and ring
57Fe shifts
of acetylferrocene
by dielectric
relaxation
The tilting
[44). has been
measurements
265 at 100 MHz-38
GHz and 293-323K
intermolecular
association
observed
between
molecule
exhibited
the solute
axis perpendicular
Ii451 -
around
the molecular rings or to
reorientation.
Similar
found between constants
An attempt residence motion
showed
neutron
the different
techniques
were
rings
considered
of ferrocene radical
to
formed within
give
Electrodes cations
reversible
between
kinetic
ferrocene
that anionic non-ionic
micelles
The intermediate the reaction
in the presence
by picosecond
oxidation
absorption
and decayed
of the diphenylmethyl
and the diphenylmethyl
cation
inhibit
the transfer
the process
and T~(OAC)~
has been
the
in ivater [50].
while
[sl].
cationic
and
The reaction
of a kinetic
species
study.
was hydrolysed
to give the observed
conditions
reaction
has shown
to form 1-ferrocenyl-1,
the subject
methoxythallation
conditionsused
[kg].
and octyl-ferrocenium
and used to determine
and octyl-ferrocene
catalyze
Under the same reaction
Referencesp.317
[48].
study of the electron-transfer
vinylferrocene
2-dimethoxyethane
when the three
and {Co(l,10-phenanthroline)]3+
micelles
energies,
ion and the diphenylmethyl
to dipropyl-
of dipropyl-
A stopped-flow
between
ferrocene
phase
of activation
35~s of the photolysis
have been constructed
solubilities
order-disorder
studied
at the same rate by ferrocenium radical
and calorimetry.
has been photolysed
The ferrocenium
were
of metallocenes,
of the solid state reorientational
together
and the reaction
spectroscopy.
and X+(R)
could only be derived
Diphenylchloromethane
was
by vibrational
scattering
that the determination
times and geometries
of aromatic
On application
A series
has been studied
quasielastic
to classify
transitions
[47].
vibrations
correlation
of C=O vibration
fragments
ferrocene,
a linear
were
The effect
valence
has been investigated.
the wavenumbers
included
of carbonyl
equation
and l,l'-
obtained
[46].
for acetylferrocene
Duyse
of structural
spectroscopy,
was observed
The results
on the wavenumbers
derivatives
behaviour
were made on benzoyl-
in E-xylene.
of the Seth-Paul-Van
which
Debye-like
to those observed
in ferrocene
to rotation
measurements
of substituents
The acetylferrocene band in the GHz-region
to the two q-cyclopentadienyl
-dibenzoyl-ferrocene similar
either
No
of any type was
molecules.
one sharp absorption
and this was assigned molecular
at low concentratians.
or interation
under
product.
P-methylvinylferroce
gave
266
both addition
and substitution
The effect of ferrocene substituted centration
trans-stilbenes
products
[52].
on the photoisomerization has been investigated.
of The con-
of the cis-isomer formed at equilibrium in the
photoisomerization of the trans-isomer (4.12; Rl = MeO, R2 = N02) was decreased by the presence of ferrocene. This was taken to indicate the participation of a triplet state, Ferrocene had no effect on the photoisomerization of the trans-stilbenes [4.12; R1 = NMe2, R2 = P(0)Ph2, Br] [53]. The R2
vapour pressures of benzoyl- and l,l'-dibenzoyl-ferrocene have been measured by a torsion-effusion technique. The pressure-temperature equations were derived and second-law treatment of the data produced the heats of sublimation [54]. When single crystals of ferrocene were cooled below the X-type phase transition at 163.9K, crystal disintegration occurred with explosive violence. The strain energy released at the disintegration was 1.10 kJmol-1. The disintegration was explained in terms of an energy transfer from the strain energy accumulated in the domain boundaries in a form of elastic energy to the kinetic energy of disintegrated crystallites [55]. The phase transitions of ferrocene-d10 have been examined. The high-temperature phase was easily undercooled to give a A-type transition at 164.1~ in the metastable state. The stable low-temperature phase was obtained by annealing the undercooled A first-order phase transhigh-temperature phase at 190K. ition occurred between the stable low-temperature and highA new low-temperature temperature phases at 25lK [56]. crystalline phase of azaferrocene stable at <28x has been found from the measurements of proton spin-lattice relaxation
267
time and differential 5.
ELECTROCHEMISTRY The operation
with polymer ferrocenes
thermal
AND PHOTOSENSITIVE of electrodes
ELECTRODES
chemically
films has been the subject
were among
neopolarographic polymerized
[57].
analysis
chemically
modified
Small band gap semiconductor electrodes, L-591 * and In203 glass electrodes, have been chemically the surface-active
redox
couple
electrodes to anchor
carboxylic
the active n-Type
way [60].
and l.OM lithium
ferrocene
silicon
open-circuit
arsenide
The properties
and rotation
of two-layer
References p. 311
in aqueous
the Fe3+/Fe2+
and
in acetonitrile.
in
solutions
The values
from water
containing
and 0.22V [63].
to light.
wafer which was
polymer.
The polymer with
has been determined
(111) single-crystal
photoelectrochemical
and I/I- redox
The
has been carried
of poly(chloromethylstyrene) The stability
has
of the under
exposed
silicon
coated
of
The electrochemical
of ferrocene
crystal
ferrocene-polypyrrole
electrodes
containing
[64].
using n-type
photoelectrode
a semiconductor
single
by the treatment
a lithioferrocenophane
[Sl].
hexacyanoferrate(I1)
coated with a ferrocenophane was prepared
[62].
n-silicon
of hydrogen
out by using as the cathode The cathode was a R-type
of 10.1% A high
disc electrodes
and K4Fe(CN)6-NaC104
of potassium
generation
ion
were -examined as a function
velocity
by cyclic voltammetry.
in the presence
silicon
rotating
in
in this
with 0.2M
efficiences
with ferrocene
were 0.3lV in the presence
photoassisted
in methanol
serving
stability
into electricity.
silicon
of a gold modified
been examined potentials
Electrode
exhibited
perchlorate
ferrocene-Et4NC10q-C2H50H
of
l-hydroxyethylferrocenium
of the electrades
light intensity
complexes
cell has been constructed
or p-type
tetrabutylammonium
by
complex
of 0.53V was also achieved
An electrochemical
such as n-Si modified
cells was enhanced
electrodes
0.5mM
electrode
was used to modify
the chromium
group.
of sunlight
voltage
of chromium
Ferrocene
with
perchlorate
for the conversion
behaviour
acids.
photovoltaic
l-hydroxyethylferrocene,
gallium
properties
by this procedure
photoelectrochemical
Poly-
Cyclic
have been used to study a plasma-
vinylferrocene-film
using
by coating
of a review.
used [58].
the polymers
methods
modified
couples
cells
[65].
268 l,l'-Diformylferrocene poly(l,l'-ferrocenylene
(5.1) has been used to prepare
vinylene
phenylene
vinylene)
(PFVPV)
PFVPV was an insulating material with a high resistivity (5.2). but on oxidation (doping) with iodine, bromine or arsenic (V)
CHO
Fe
+
DMF
Ph3P=s-PPh3
CHO
5.1
n
fluoride
it became
a semiconductor with conductivities ranging -1 Iodine doped material underwent an .
from 10 -4 to 10-gRcm instantaneous
two-fold
increase
in conductivity
when illuminated
75W tungsten lamp [66]. Ferrocene monomers such as the unsaturated ketones (5.3; Y = Cl-Cl0 alkylene, carboxyl,
witn
a
alkylenoxy)
have been converted
to crosslinked
to form a gel in an electrolyte. was a semiconductor, illuminated
were immersed
to form a photovoltaic
polymers
Two electrodes,
in the electrolyte device
and used
one of which
[67, 681.
and The poor
269
Y-NHCOCH=CH2
Fe
Y-NHCOCH=CH2
5.3
charge
transfer
the oxidation couple
characteristics
and reduction
have been attributed
difficulty electrode
surface
electrodes
using
which
transport.
limited
[69].
carbon
by an argon
plasma.
were studied
charge
films the reactions (T-Me5C5)2M,
and their structures ring enhanced
and all the metallocenes nature
studies
where M = V,
investigated
verified
of the following
investigated.
its ligand were
low
the reversibility
process
where
M = Cr,
Mn, Fe, Co, Ni: (I-Me5C5)~M~[(7-Me5C5)2M1+ + eThe incorporation of an ionic dye (croconate poly(vinylpyridine)
coated
electrodes
significant
Ftefemncesp.817
were
[70].
Cyclic voltammetry
produced
electrooxidation
via
and the ferrocenium
of electrochemical
of the I-cyclopentadienyl
and one electron
on glassy
ferrocene
of decamethylmetallocenes
field strength spin.
of the
covered with a thin film
of thicker
Cr, Mn, Co, Ni, has been prepared Alkylation
This
previously
between
hindrance
In the presence
A series
for
derivatization
of the electrodes
On an electrode
without
used
instability.
polymerized
properties
the redox reaction
ion proceeded
electrodes
1,1' -ferrocenediyldichlorosilane
had been etched
cyclic voltammetry. of polymer
by chemical
has been plasma
The electrochemical
diffusion
to oxidative
has been overcome
Vinylferrocene
of nickel
of the ferrocene-ferrocenium
of soluble
polycrystalline changes
ferrocene
c711 violet)
into
tin (IV) oxide
in the kinetics
derivatives
[72].
of A
270 reversible
cyclic voltammogram
of ferrocene
for the one-electron
in 1,2_dimethoxyethane
conditions
that enabled
minutes.
The formal rate constant
the ferrocene
with
pentadienyl including
ligand
half-wave
that the ferrocene
potentials
iron through
0
anion
diferrocenyl
varied
compounds
n = 0, 1 and 5.5) have been the study using platinum
difference between
acetonitrile,
acetone, Iron-to
Several
(5.4;
of an electrochemical The
-1
10'1 ems
and one planar pentahapto-cyclo-
[73].
the ketones
voltammetry.
x 10e3 cm s-1 which which was
it was postulated
had one bent tetrahapto-
subject
anion to exist for several o/-
that of ferrocene
From these results
under
of the ferrocene
at -45'C was approximately+;;7
electrode
was compared
reduction
has been recorded
the first
by >4OmV
electrode
and second
in solvents
such as methanol,
dichloromethane
and nitromethaae.
space interaction
was not important
[74].
~cocH2CcH2)n~
e
6
6
0
0
5.4
The effect Moessbauer
of carbonyl
spectra
acetylferrocene, increased in ketone ethylene spectra
group O(to
the oxidation
approximately
(5.7) reached
of the ketoferrocenes
charge-transfer
and the ketones
The results
were smaller
of ferrocene
ring
indicated
group through
splittings
shifts were approximately kinetics
(5.6
effect of the carbonyl
the ferrocenyl
The quadrupole
and
in formylferrocene,
the I-cyclopentadienyl
potential.
5O‘j“j' of the inductive
moiety.
but the isomer
on the redox potentials
ferrocenylphenylketone
A carbonyl
and 5.7).
groups
has been investigated
that group
the
in the Moessbauer
than that of ferrocene
the same [75].
at platinum
The
and vitreous
271
CH=CHCOPh
COCH=CHPh
Fe
Fe
5.6
carbon
5.7
electrodes
have been determined
chronocoulometry. of the electrode LiC104,
and solubility
quaternary cyanide
and of the supporting
Et,+NC104 or Et4NBF4
diffusion
ammonium
[ 763.
salts
melt electrolytes.
chloride
ion attack
occurred.
In acid melts, an intramolecular centre
carbon
electron
[77].
heterogeneous -crystal solvent
of the hole [79]. water
nucleophilic
ferrocenecarboxylic
(vinyl ferrocene)
between
[78].
potential increase
(5.8)
passed during
R.eferencee p. 817
through
on
acid
It was and
The rate of
a laser-excited
single-
and ferrocene in a non-aqueous -1 as a first-order constant
at 10 4 s
The contact
The dynamic
and
in p-cyclodextrin
angle
has been measured
in the form of a drop of O.lM potassiumchloride
electrode.
products
from the carbenium
has been investigated.
zinc oxide electrode has been determined
methyl
The effect of B-cyclodextrin between
in the cavity
hole transfer
in water,
salts decomposed
transfer
could be included
the iron atom was located
ferrocenylalkyl
ion charge-transfer
the quaternary
electrodes
that the acid
of several
In the basic melts
the rate of electron-transfer concluded
which was
alumini.um chloride-l-butylpyridinium
of ferrocenium
underwent
ion to the metal
electrolyte
have been investigated
chloride
step
were independent
Oxidation-reduction,
properties
and room-temperature
and glassy
by potential
The formal rate constants
as a film on the surface contact
angle decreased
the ferrocene
the reduction
wave
[8O].
oxidation
between
and poly-
of a platinum as the electrode wave but did not
272
n
Fe
5.8
6.
PREPARATIONS
OF FERROCENE
An improved been reported.
method
A catalytic
(2 mmol) was dissolved hydroxide
(15g) iron
(II) chloride
of these alkynes, Structural
and propyne
they were substituted with
-methoxyferrocene
(6.1).
proceeded
The helicene
[82].
cyclopentadienide
indicated
that
of (&
g>-
1,3-diphenyl-2-
that this reaction
to the differences
on indene and fluorene
which was
of the pentamethyl-
and is appreciably ion.
inchemistry
metal
to the helical
dianion
The basicity
ing (I-pentamethylcyclopentadienyl)
in a 13-step
and converted
ion has been determined
(q-cyclopentadienyl>transi.tion
All
(6.2) [83].
than that of the cyclopentadienide
has been related
61%) [81-j. 3-hexyne,
The reaction produced
(2.4) by way of the corresponding [841.
was
iron complexes.
(6.3) has been synthesized
treated with FeC12.2THF
methylation
2-pentyne,
It was postulated
from 2,7-dibromonaphthalene
ferrocene
(approximately
produced
(?-C5H5)Fe(CO)21
via the ferrabenzene
mmol) and
The mixture
of the iron complexes
ferrocenes
-PhCLi=CHCH=CLiPh
(33
sodium
have been investigated,
except propyne,
characterisation
has
glycol
powdered
tetrahydrate
mmol) were added.
of iron atoms with 2-butyne,
methylphenylacetylene
greater
of polyethylene
for one hour to give ferrocene
The reaction
process
amount
of ferrocene
in dimethylsulphoxide,
(67
1,3_cyclopentadiene stirred
for the preparation
complexes complexes.
This difference between and the correspondThe effects
of
ligands were also discussed
[85].
273
Ph
Fe
6.2
6.1
6.3
7. REACTIONS
OF FERROCENE
A study has been carried by olefinic produced
generated
ethylferrocene
in concentrated diazonium
[86].
hydrocarbons
ethyl radicals,
and diethylferrocene
salts prepared
with 2-methyl-5-
The reaction
[87].
Ferrocene
amines
and l,lfi-di-substituted
and -6-benzothiazolyl,
with
at 205-230°,
acid has been treated
from heterocyclic
Mono-
of ferrocene
of ferrocene
from diethylmercury
hydrochloric
cenylheterocycles.
out on the alkylation
with to give
ferro-
ferrocenes
2,3,3-trimethyl-5-indolenyl,
2-methyl-5- and -8-quinolyl groups were obtained [88]. A series 6 of (7 -arene)($-cyclopentadienyl)iron cations has been prepared from ferrocene Ligand
exchange
Rsferencesp.317
and subjected reactions
to a spectroscopic
between
ferrocene,and
study [Sg]. dibenzodioxin,
274
Q0
2+
Fe
Fe
h
Fe
0
7.1
phenoxathiin
h
or phenoxazine
-cyclopentadienyl)iron
produced
cations
X = NH, Y=S) respectively. complexes excess
was compared
of ferrocene
corresponding dications
reversible organic
carbon
intercalation detonation
and provided
process
[ql].
when mixed with
the
of ferrocene,
dioxide
fluoroborate
the basis of a Tetranitromethane
ferrocene
Thus tetranitromethane,
in solution
O.Olg, was mixed
contained
and nitrous
nitrogen,
oxygen,
oxide [92].
carbon
The hydro-
have been displaced
to form pentakis(trifluorophosphine)iron
tetrafluoroborate
from ferrocene
and HBF4.0Et2
in
0.2m1, when an explosion
SALTS AND MIXED-VALENCE
Ferrocenium yield
reaction
have been used as oxidizing
in bis(pentadienyl)iron
trifluorophosphine 8. FERROCENIUM
When a large
exchange
Thus stage 5 graphite
The gases evolved nitrogen
ligands
route.
of these
[90].
compounds
ferrocene
solvents.
occurred.
x=s, Y=O;
of preparation
with an alternative
ferrocene.
with a 2oo/osolution dioxide,
X=Y=o;
This method
(7.2) were obtained
oxidized
underwent
the (q6-heterocycl_e)(15-
(7.1;
(q6, 76-heterocycle)bis($-cyclopentadienyl)
towards
smoothly
7.2
was used in the ligand
Graphite-acceptor agents
0
SALTS
has been prepared in nitromethane
in 93%
[94].
by
[93].
275
8.1
The heterogeneous in saturated
oxidation
hydrocarbon
of ferrocene
solutions
solution
of ferrocene
and bismuth(II1)
oxidized
by molecular
oxygen
ferrocenium -black
by X-ray
precipitate.
-valenceT(-bond -ferrocene
spectra bridged
compounds.
Q Fe
8.2
in acetone
of sunlight
which
A was to the
formed a blue-
The salt was characterized
have been recorded and 6-bond
Intervalence
bridged
for nineteen
mixed-
di-, tri- and tetra-
electron
0
Fe
(IV) oxide
[95].
[96].
crystallography
The near-IR
bromide
in the presence
salt [(7-CsH5)zFe]q[Bi4Br16]
crystalline
on manganese
has been studied
Fe
8.3
transfer
was evident
276
in all of the Z-bond species.
derivatives transition through
was attributed
space mechanism.
Among
transfer
azoferrocene,
transition (8.2;
compounds
(Sol),
CH=NN=CH, spectroscopy. 8.3;
n = 1;
were characterized [‘8].
[97].
ferrocenes
by cyclic voltammetry,
and Moessbauer
includi.ng (8.2;
at room temperature
the
and diferrocenylketone CPh=CPh,
the
to a
exhibiting
= 13, tetracyanoquinodimethane,
-5,&dicyanobenzoquinone)
while
1,2-diferrocenylethene
CMe=CMe,
spectroscopy,
n = 1, X
mechanism
n = 1, 2) and the bridged
of the complexes
bridged
bridged
was attributed
the compounds
were,
n = 1, 2) have been studied
IR and electronic
CPh=CPh,
compounds
l,l-diferrocenylethene
Y = Hg, PPh, CH=CH,
CMe=NN=CMe,
in the?t-bond
to a through-bond
bridged
The biferrocenes
Several
and some of the f-bond
transition
in the c-bond
electron
(8.3;
bridged
The near-IR
Y=
2,3-dichloro-
as mixed-valence
Cyclic voltammetry
and
8.4
visible
and near-infrared
electron
transfer
complexes
(8.4;
series 2+/+/O/-
inthe
spectroscopy
ferrocene-tricobalt
R = Me, Ph). with specific
electrode
species were stable.
electrolysis
were used to obtain
found that both the ferrocenyl cations
[l+,O]
observed
intervalence
had localized were
however
oxidation
the cationic
moiety
transitions
formed a redox
potentials,
Chemical
species,
only
and it was
and the Co3C cluster
as redox sites in the dications
-valence
carbon cluster
Both complexes
the cationic
behaved
have been used to examine
[l+,l+]. valence
The mixed-
sites and the
consistent
with the Hush
277
model
for a class II species
electron
transfer
Decomposition Fe-C2(CN)4
optical
where
(v-C5H5)25 . phase of the
to be a ternary
D and A are donor and acceptor
type [D+][Do_5A-3, respectively. The crystal found to be composed
complex
gave the salt [(q-C5H5)2Fe]r
which was considered
(i) ferrocenium
unsymmetrical
of the charge-transfer
in ethyl acetate
[(NC),C=CCNO]'
displaying
C-91.
structure
was determined
c;' one-dimensional
segregated
ions and (ii) alternating
(tricyanoethenolate)2:ferrocene
stacks
1:2:1
molecules
and it was
stacks
of;
ferrocene:
[loo].
The &-
Ph
Ph
and
8.5
(8.5 and 8.6)
trans-isomers reactions
at almost
underwent
the same potentials
and these were attributed indicative
that the intervalent interaction possible
The
transfer.
It was concluded from a Co(I)-Fe(II1)
arose
in the 2+ ions because
Fe-Fe interaction
was not
[loll.
9. FERROCENYL Several
CARBENIUM
(9.1;
Referenceap.317
IONS
diferrocenylcarbenium
Ph, X = BF4,C104) the salt
couples.
gave rise to a band in the near
of intervalent transfer
redox
in the range 0.30-0.55V
to the Fe(II)-Fe(II1)
l+ and 2+ ions of both isomers infrared
two successive
salts
have been prepared
(9.2;
by heating
R = H, Me, Et, Ph, X = BF
4'
R = H, Me, Et, ferrocene
with
C104) in acetic
acid.
+ I 1
278
_
Fe
CR+
X-
Fe
2
9.2
9.1
The salts ponding double metal
(9.2) underwent
9.3
alkaline
diferrocenylmethanols resonance
technique
participation
ferrocenyl
in the stabilization
participation.
chemical
a sensitive
Factors
shift differences
rehybridization
were
caused by the electron in the cyclopentadienyl
were the cations
hydrolysis aqueous
(9.3;
ci-deuterium kinetic
significant
cyanide.
bonding
ligand.
n = 3;
chloride
in water
containing
ion [104].
other metals
metal
complexes
(metalloids) [lO.l;
n = 21 has been prepared
Mn(II),
of acetoacetylferrocene
with Fe(N03j3,
by the
Cu(OCOCH3),
Ferrocenyl-@-diketonate
respectively
ligands
R = Me, CF3) have been used to prepare
zirconium titanium
and hafnium complexes
[105].
M = Fe(II),
and Mn(OCOCH3)2 (10.2;
and
that there was no
the iron atom and the c(-carbon atom
of transition
M = Cu(II),
reaction
A large
effect has been found on
CHEMISTRY
(i) Derivatives A series
effect of the Among the species
R = H, Me, Ph) [103]. isotope
in the ferrocenylmethylquinolinium 10. FERROCENE
the large
effect caused by
withdrawing
It was concluded
between
a
cJ-orbitals and
of ferrocenylmethylquinolinium
methyl
direct
for the evaluation
the shielding
of the iron non-bonding
substituent studied
tool
spanned
active in producing
deshielding
secondary
NMR
of 57 Fe-enriched
The 57 Fe resonances
carbocations.
to the corres-
The 13C{57Fej
has been used to investigate
1200 ppm range and provided ofiron
hydrolysis
[~oz].
complexes.
(10.3;
titanium,
The bis(7-cyclopentadienyl)-
R = Cl, CH2NMe2)
were also prepared.
279
-0c I
0
‘0 --, -
COCH2COR
0'
Fe
M
6
Fe
COCH2COR
0
n .
10.1
10.2
The complexes were characterized by mass spectrometry [106]. 7 Reaction of the ferrocenyl-hydrazones (10.4; RL = H, Me; R2 = Ph, ~-cl-, E-NO~-, E-HO-C~H~, 4-pyridyl) with copper(U) acetate produced the corresponding copper(I1) complexes (10.5) c1071.
Reaction of the ferrocenylhydrazones (10.6;
_4A-p 6
:'@J
R = Ph,
~I'NNHCOR~
6
-L 10.3
10.4
4-ClC6H4, 2-02NC6H4, 2-HOC6H4, pyridyl) with tin(I1) chloride or R2Sn0, where R = Bu, octyl, produced the corresponding coordination complexes (10.7; R1 = Ph, 4-ClC6H4, 2-02NC6H4, 2-HOC6H4 , pyridyl; R2 = Cl, Bu, octyl) [108]. The same ferrocenyl-hydrazones (10.6) also formed stable complexes with triphenyltin acetate. The structure of the complex depended
RefeIe.ncesp.817
280
CH=NNHCOR
Fe I Fe
0 0
10.6
on the substituent tin(W)
complexes
species
[109].
Terminal conditions
R.
Both octahedral
and trigonalbipyramidal
were
formed together
with acetoxy
olefins
have been hydrogenated
bridged
under mild
by using dichloro(triphenylphosphine)[l-(N,N-o(-dimethyl-
aminoethyl)-2-diphenylphosphinoferrocene]ruthenium(II) catalyst
[llO].
Several
substituted
Fe
ferrocenylnitriles
as a have been
281
prepared and used as ligands to form (NH3)5Ru(II)nitrile complexes in which intervalence transfer was investigated by electronic A weakly coupled Class II description absorption spectroscopy. was used to account for the observed behaviour [ill]. The
10.8
10.9
hydroformylation of ally1 alcohol has been carried out using several rhodium-phosphine catalysts. l,l'-Bis(diphenylphosphinyl)ferrocene was found to be one of the efficient phosphines in the catalyst [112]. The hydroformylation of 1-hexene in the presence of HRhCO(PPh3)3-bidentate phosphine ligand catalysts has been investigated. A good linear Hammett free-energy relationship was obtained for 1,l '-bis(diarylphosphino)ferrocenes with electron withdrawing substituents. These catalysts gave higher rates and selectivities to linear aldehyde formation [llf. The (z)- and (-)- ferrocene-palladium complex (10.8) has been treated with the sodium salts of several amino acids, RNHCHMeC02Na, to form the amino acid and dipeptide complexes R = H, NH2CH2C0, NH2CHMeCO) [114]. The optically (10.9; active ferrocene analogue of prostanoic acid (10.12) has been prepared from the ferrocene-palladium complex (10.10) by way of the intermediate keto-ester (10.11) [115]. Organozinc reagents, prepared from the reaction of secondary alkyl Grignard reagents (ArRCHMgCl, where Ar = Ph, E-MeC6H4; R = Me, Et) and excess zinc halides were treated with vinylbromide in the presence of the chiral ferrocenylphosphine-palladium complex (10.13) as The asymmetric cross coupling products (10.14; a catalyst.
282
NMe2 I
IEt3SiH
Fe
10.12
R1 = H, Me, R2 = Me, Et) were obtained excess
[ 1161.
The enantiomeric
formed complexes L-aspartic diglycine produced
glycinate
complex
[117].
with the acid chlorides Treatment
produced
The benzoylation
combined
palladium
of ferrocenylcopper Acylation
64
derivative
ethylenediamine
complex
(10.8) L-lysine,
XC H COCl, where X = E-B', E-MeO, the corresponding
Slow crystallization produced
The glycine
and some biferrocenyl.
of ferrocenylcopper
diferrocenyl
complex glycine,
to form a hexacoordinated
benzoylferrocene
g-NO2, z-No2,
dipalladium
with amino acids including
acid and L-cysteine.
with sodium
in up to 86% enantiomeric
ferrocenylketones
with adipoyl
chloride
(10.15).
gave the
(10.16) [11_8]. of the dilithioferrocene-tetramethyl-
(T?'IEDA)adduct
(10.17)
from ether solution
[(7-C5H4Li)Fe(7-C5HjLiCH(Me)NMe2)]~[LiOEt]2[TMEDA]2.
283
Me
Fe
10.13
10.14
The structure of this latter complex was determined by X-ray The structure consisted of discrete molecules analysis. possessing exact C2 symmetry; each containing four ferrocene moieties, ten lithium atoms, two TMEDA units and two ethoxy groups. Each of the five independent lithium atoms achieved a distorted tetrahedral coordination in a different way. An extremely short Li-C bond (2.048) was observed [119].
qco
ax
~co’cH2’4c~
Fe
10.15
10.16
Treatment of thel,l'-dilithioferrocene (lo.181 with mercury(I1) chloride produced the ferrocenophane (10.19) [1201. Lithiation of 1,2,3,4,5-pentamethylferrocene (10.20) followed by condensation with tetrachlorosilane produced the ferrocenophane (10.21).
R8fsrsacap.917
284
10.17
This
10.18
ferrocenophane
was used to derivatize
platinum
and n-type
silicon
platinum
electrodes
exhibited
waves
consistent
electrodes
2 (cyt Cox)
The functionalized oxidation reduction
the one-electron n-type
redox couple.
reauction
photoanodes
of cyt sred upon illumination in the dark.
cyclic voltammetry
to ferrocytochrome
silicon
C (cyt Cred) effected
electrodes
2
10.20
These
of horse heart
and effected
The derivatized
CH2NMe 10.19
of
The functionalized
persistent
with a surface-confined
effected
ferricytochrome
electrodes.
the surface
the uphill
cyt sax were durable
285
Fe
Sic12 10.21
10.22
and lost little activity with repeated use [121]. Metalation of azaferrocene with n-butyllithium gave a mixture of 2- and l'-lithio- and the 2,1'-dilithio-intermediates which were characterized by treatment with methyliodide 'cogive the corresponding methyl- and dimethylazaferrocenes. The predominant product was the 2-methyl compound (10.22) [122]. The phosphonoferrocene (10.23; Y = OH) has been treated with triphenylphosphine in HBF or in HClO and CH Cl to form 2 2 4 4_ the phosphonium salts (10.23; Y = PPh;BF4 , C104-) respectively
Q-
9
FHP(OEt)2 Y
0
F;e
t,
Q0
9 ?ph3
CP(OEt)2
Fe
c!l
0
0
10.23
References p. 317
10.24
286
Fe
1
.
Fe
PX
6 0
6
which were converted
by sodium
secondary
phosphine
hydride.
Several
(10.25; related
X = Cl) was reduced
(10-25;
iodide
was converted
the alkali
spectra alkali of
cations
complexes indicated
ferrocenylmethylchloride
produced
the diquaternary
hydride
M = Na, K).
solvents group.
These
and the NMR between
the
The reaction
with bis(diphenylphosphino)methane
salt
(10.30).
salt with strong bases was investigated Mono- and di-phosphaferrocenes, compound
(10.28)~
an interaction
and the ferrocenyl
with
the phosphonium
or potassium
(10.29;
in some organic
of the solutions metal
were reported
produced
produced
metal
to the
aluminium
into the ylide
of this ylide with sodium amide were soluble
(10.26)
by Moessbauer
X = H) with lithium
Reaction complexes
x = Cl)
of bis(diphenylphosphino)methane
[ 124, 1251. ferrocenyltri.methylammonium (10.27) which
(10.24)
(10.25;
to form the salt
compound
transformations
The reaction
salt
to the ylide
chloride
chloride
as a ferrocenyl
The chloride
2
carbonate
[ 1231. has been treated with aluminium
spectroscopy.
4
10.26
The ferrocenylphosghorus(II1)
which was confirmed
AlCl -
0
2
10.25,
P"
(10.31) have been studied
The reaction
of this
[126].
including
the tetraphenyl
by 'H and 31P NMR and
Introduction of a phosphorus atom into Moessbauer spectroscopy. the cyclopentadienyl ring caused a reduction in quadrupole splitting
by comparison
(10.31) underwent high quadrupole
with
ferrocene.
phenyl ring protonation
splitting
terms of iron participation
The diphosphaferrocene in CF3S03H
and the
for this species was interpreted in the stabilization
of the
in
+
287
cH2P(Ph)2=CHPPh2
H,P(Ph),CH,PPh2 IFe
Fe
10.28
10.27
2c1-
10.29 6-complex
[127].
10.30
The preparation
5-cyclohexadiene)metal
complexes
of the l,+dibora-2,(FcBC~H~BFC)M(CO)~,
Fe
10.32
Refexencssp.317
where
288
M = Cr, MO, W, and (FcBC6H4BFc)M(CO)3, has been described. benzene
moiety
v6-bonded
(ii) General
In all these complexes
(10.32) behaved
ligand
where M = Fe, Ru, OS,
as a strongly
the 1,4-diboraback-donating
[128]. Chemistry
The ferrocenylmethylthio-carboxylic Rl = H, R2 = CH,2C02H, C6H4.C02H-2)
acids
(10.33;
have been converted
to
CHR1SR2
10.33
formylferrocene
by oxidation
of the carboxylic
acids
Rl = Me, R2 = CH2C02H)
with manganese
(10.33;
dioxide.
Reduction
RI. = H, R2 = CgH4.C02H-2;
gave methyl-
and ethyl-ferrocene
respectively [129]. The base catalysed condensation of formylferrocene with g-(CH3CO) C H produced the cyclic ketone 264 was obtained. (10.34), in th e presence of acid the olefin (10.35) Similaracid and base catalysed condensations were carried out with g-CH3COC6H4C6H4COCH3-g and 1,8_diacetylnaphthalene [130]. Treatment of acetylferrocene with POC13 and Me2NCH0 gave a
10.36
10.37
mixture of the chlorovinylferrocenes (10.36; R = H, CHO) which gave ferrocenylacetylene with sodium hydroxide. Ferrocenylacetylene was coupled in the presence of copper(I1) to form the diacetylene (10.37) [131-j. Decomposition of the dicarbonyl compound (10.38) with 1:l MgBr2-Mg(OMe)2 or MeOMgBr produced
HOMe F Ph Fe
10.38
Referencen p. 317
10 -39
10.40
220 the ether (10.39) as the major product. In a similar decomposition with C5H10NMgBr the amine (10.40) was obtained [l32]. Ferrocene polyethers (10.41; n = O-3) have been prepared by treatment of l,l'-diacetoxyferrocene with the halid,es Me(OCH2CH2)nX, where X = halogen. Ths polyether (10.41; n = 3) was effective in the extraction of unipositive cations. The order of efficiency was: Ag+> Tlf> Cs+> K+> Li+> Na+ The diferrocenyl polyethers (10.42; n = 2-4) were obtained by treatment of the potassium salt of hydroxyferrocene with the dibromides Br(CH2CH20)nCH2CH2Br in DMF. These polyethers (10.42) were not useful as extractants for metal cations [133].
Q-
0(CH2CH20),CH2CH20
0
Fe
Fe
Fe
10.41
10.42
p-Dicarbonyl derivatives of ferrocene have been used to prepare the ferrocenylheterocycles (10.43; 10.44 and 10.45; Ferrocenylmethyl compounds (10.46; R = H, Me, Ph) [134]. R = Me, Ph, ferrocenyl) have been oxidised to the corresponding ketones (10.47; R = Me, Ph, ferrocenyl) with bis(triphenylFerrocenylethenes were silyl)chromate(VI), (Ph3Si0)2Cr02. oxidatively cleaved by the same reagent to aldehydes [135]. Oxidation of the alcohols (10.48; R = H, Me, Ph, substituted Ph, OMe, CMe3) to the corresponding ketones (10.47; R = H, Me, Ph, substituted Ph, OMe, CMe3) has been investigated using [Bu~N]~[C~~O~], [PhNH3][Cr03C11 and [Bu4N][Mn04] as the Acylferrocenes have been treated with thioreagents [136]. glycollic acid and the ethyl ester to form the dithio compounds l,l'-Diacylferrocenes (10.49; Rl = H, Me, Ph; R2 = H, Et).
291
Fe
10.44
10.43
10.46
10.45
Reduction of the compounds (10.49) underwent the same reaction. with lithium aluminium hydride gave the corresponding diols
Q-
COR
0
Fe
10.47
Raf-p.817
Q-
CHROH
0
Fe
10.48
292
Q-
R1(SCH,C02R2),
CR(ASCH~CH~OH)~
0
10.50
10.49
(10.50;
R = H, Me, Ph) [137]. catalytic hydrogenation
The
diethylferrocene Ti,Fe-Ti, active
Cr-Ti,
catalysts
on nickel-aluminium-metal Cu) has been investigated. was obtained
of diacetylferrocene
1,2-disubstitvted
[139].
ferrocenes,
R1 = Me, R2 = (cH~)~oH] [10.51;
pressure
Enantiomeric
(metal =
One of the most
catalyst
of hydrogen
Hydrogenation in propan-2-01 gave 85-98s
and diastereomeric
for example
have been prepared
R1 = CO(CH2)5C02Et,
t0
catalysts
when M = Ti [138].
on a nickel-rhenium
at 78'C under one atmosphere diethylferrocene
of diacetylferrocene
the alcohol
R2 = H] via reduction,
amination,
. >5C02Et
Fe
R2
I 2
10.51
10.52
rlO.51;
from the ester
293
~cH2cH20H
p
Fe
Fe
Fe
cyclopalladation
with sodium
(10.52)
amination
[140].
ferrocene
with phosphorus(II1)
produced
of this cyanide
followed
tetrachloropalladate(I1)
the dimer
cyanide
by carbonylation
The reaction
chloride
of the diacid
by potassium Hydrolysis
obtained [141].
such as the secondary
R = Me, Ph) have been converted
gave the
The cyanide was also used
l,l'-bis(@-aminoethyl)ferrocene
Ferrocenemethanols amines
followed
l,l'-bis(cyanomethyl)ferrocene. and reduction
to give
and reductive
of l,l'-bis(hydroxymethyl)-
(10.53) in 56% total yield.
to prepare
10.55
10.54
10.53
diol
ph:
CHROH
to the corresponding
(10.55; R1 =. Me, Ph, R2 = Me;
(10.54;
alcohols
tertiary
Rl = Ph, R2 = Et) by
_
Q-
1
CHMe
0
Fe
. 10.56
Referencea p.
317
10.57
NH
n
10.58
3-n
Fe
lG.61
10.60
10.59
treatment with hydrogen bromide and then dimethylamine or diethylamine [1423. Treatment of l-ferrocenylethanol (10.56) with dimethylamine and dicyclohexylamine in the presence of hydrogen bromide gave the tertiary ferrocenylethylamines (10.57; When the reagent was ammonia a mixture of the R = Me, C6Hll). primary, secondary and tertiary amines (10.58; n = 1, 2, 3) was Use of the optically active amine d-(+)-PhMeCHNH2 obtained. led to the formation of diastereoisomeric ferrocenylethylamine Dehydration of the alcohol (10.59) with products [143]. SnC12-HCl gave 96% of the trans-isomer of the olefin (10.60). When a mixture of the cis- and trans-isomers was treated with
Q0
FHcHzoH OH
Fe
0
6
10.62
10.63
Q-
NHCOCH3
NCOCH3
NH
0
1. NaNH2 Fe
Fe
2. FcBr, CuBr pyridine
KOH EtOH
>
10.64 10.67
10.66 / KOH
1. NaNH2
H2°
2. FcBr, CuBr pyridine /
Q-
NH2
0
Fe
6 0
10.65
3 10.68
SnC12-HCl, 94-5% of the trans-isomer was produced (10.60). Reaction of the cis- and trans-isomers with H202-KOH produced the cis- and thexans-acrylamide (10.61) [144]. Oxidation of vinylferrocene with tetrabutylammonium permanganate in dichloromethane produced the diol (10.62) [145]. The hydrazides (10.63; R1 = H, R2 = Et, Br, Ph; Rl = Me, R2 = Ph) have been prepared from ferrocenoyl chloride and z-RlC6H4NHNHCOCR;OH [1461. The reaction of bromoferrocene with the sodium salt of an amine or amide in the presence of copper(I) bromide/pyridine has been used as a general method for the preparation of Ferrocenylamine (10.65) was prepared by the ferrocenylamines.
296
Fe
6
0
"MN
2 lo.69
hydrolysis
10.70
of N-ferrocenylacetamide
(10.67) and tertiary
(10.68)
from the same starting diferrocenylamide
(10.64).
ferrocenylamines
material
the intermediate
The reaction
of chloromethyl-
(10.66) [147].
the corresponding
and 10.70)
photooxidation
with 4,4'-bipyridine
ferrocenylmethyl
Inhibition
[148].
by aliphatic
of ferrocenyl-substituted
been reinvestigated.
The aliphatic for OH radicals
the oxidation
[149].
11. BIFERROCENES,
FERROCENOPHANES
The electronic iene
structures
The results
semiempirical ization
were
which
derived
(11.1) has been estimated. ferrocenes theoretical crystal
to be classified models used
and molecular by X-ray
FERROCENES
spec-
calculations
predicted
using
large reorganlocalized
MOs
The time of hole exchange from biferrocene
This has allowed
for mixed valence
structure
the binuclear
species
of a picrate cation
crystallography.
in
and the complex
in a way that corresponds
salt of the [O.O]ferrocenophanium determined
in
and biferroceny-
events of highly
with major iron 3d amplitudes. the l+ and 2+ cations
AND ANNELATED
by He(I) photoelectron
for ionization
has
has been shown
which were involved
compared with
INDO MO methods
effects
(10.69
of the
carboxylic. acids
of biferrocene
(11.1) have been examined
troscopy.
derivatives alcohols
alcohol
to act as a scavenger process
were obtained
(10.64) through
and l,l'-bis(chloromethyl)-ferrocene produced
The secondary
to the
[150].
The
hemihydroquinone
(11.2) has been The Fe-Fe distance
was
297
Q-9 Fe
Fe
Fe
Fe
11.2
11.1
34 pm shortei
than in the neutral
some Fe-Fe interaction the cyclopentadienyl
ferrocenophane
in addition
rings
to the interaction
[151].
Adducts
and 1,1,2-tetramethyl[2]ferrocenophane were
prepared
by treating
X = Cl, I, CN. was strong atoms
direct
[152].
combined
with tin(IV)
[2]ferrocenophane Moessbauer of direct adducts
spectroscopy
interaction
Ferrocene, adducts
quadrupole
between
splitting
Fe-Sn bonding.
Intramolecular ferrocene
using
The red-orange
large 57Fe
which was interpreted
in terms
and [3]ferrocenophane
the ferrocenium
and
[153].
reductive
lowvalent
and [3]ferrocenophane
an unusually
The ferrocene
cations
that there
the iron and mercury
were dark green and contained
[3]ferrocenophanium
with HgX2 where
to form adducts.
showed
between
of [2]ferrocenophane
suggested
[Zjferrocenophane
chloride
indicated
with mercury(II) salts
the ferrocenophanes
Moessbauer
which
coupling
of l,l'-bis(o-formylphenyl)-
titanium reagents
gave E-
and
anti-[0~orthocyclo[2]orthocyclo[O](l,l1)ferrocenophan-7-ene~ These were
and related examined
interactions
ferrocenophanes
prepared
by NMR and UV spectroscopy between
the two benzene
of l,l'-bis(chlorocarbonyl)ferrocene the ferrocene proportions
cryptates
bis(aminophenyl)ethers (11.4;
n = 0, 1, 2).
Fl.eferenceap.317
[154].
combined
The yields
features
gave
and
by the reaction
with
to give the macrocyclic Structural
Treatment
with diaza-18-crown-6
were determined
The same reagent
reactions
for %-electronic
rings
(11.3 and 11.5).
of these products
temperature.
by similar
ethylene
glycol
ferrocenophanes
of the products
Q- T0 CON
0
0
Fe
0
0
CON
dJ
11.3
(11.3
and 11.4) and dynamic processes within the molecules were examined by 1H and 13C NMR spectroscopy [155, 1561. The diacetate (11.6; R = COMe) has been treated with the dichloroethers, ClCH,(CH2OCH,),CH,Cl, where n = O-3, in the presence of potassium hydroxide to form the chloroethers (11.6; R = CH2(CH20CH2)nCH2C1. These were then attacked by sodium sulphide to give the polyoxathiaferrocenophanes (11.7; n = O-3) and the binuclear polyoxadithiaferrocenophanes (11.8; n = O-3). The ferrocenophane (11.7; n = 3) was effective in extracting unipositive cations with the following order of efficiency: Tl+ >) Rb+, K+> Cs+> Na+)Li+ [1571* The polyoxaferrocenophanes (11.9; n = 0, 1, 2, 3, 4) were prepared in one-step by reaction of l,l'-diacetoxyferrocene with the appropriate ether ClCH2(CH20CH2),CH2Cl. The ferrocenophane n = 4) formed crystallAne 1:l complexes with lithium, (11.9; sodium and potassium thiocyanates. Spectroscopic data indicated that in these complexes there was possibly some interaction between the iron atom and the complexed alkali metal cation [158]. The polyoxa-ferrocenophanes (11.10 and 11.11; n = 2, 3, 4) and (11.12; n = 1, 2) have been prepared from l,l'-bis(hydroxyThe complexing ability of these compounds methyl)ferrocene. with alkali and transition metal cations was investigated [1591. The cyclization of 1-acetyl-l'-(&-chlorocinnamoyl)ferrocene to the ferrocenophane (11.13) was catalysed by a variety of acid The base catalyzed condensation of 1,3catalysts [160].
299
Q-
f‘ on0 /\I
CON
0
NOC
L”jJoJ
Fe
(‘ ono /\1
CON
L
-2 0
Fe
NOC
dl 0
11.5
ToI?
p&y
lt$LOR &oqAn
11.7
11.6
-ferrocenediacarbaldehyde with l,+diacetylferrocene using the high dilution technique produced the ferrocenophane (11.14).
11.8
Referencap.817
11.9
11.12
11.11
This compound hydrogenated
was reduced
with the 3-arylThe reaction
was completely
to substituents
at C(3).
giving
alkyd groups were
The chair conformation, bonding
in which
predominated
(11.17) [ 1621
have been prepared
cis
with strong
in the hydroxy-
A series
the two I-cyciopentadienyl
rings,
the corres-
R2 = Me, Et, n-Pr, i-Pr,
the introduced
hydrogen
derivatives
by biphenyl
reagents
Et) has been investigated.
(11.16) and this was the o;*ly conformer
dihydroxy phanes,
Me2CHCH2,
stereospecific
(llJ6 and 11.17;
t-Bu) where
intramolecular
[161].
of Grignard
and 3-alkyl-[5]ferrocenophane-1,5-diones
alcohols
CH2=CHCH2,
ketones
of the reaction
R1 = Ph, E-MeOC6Hq,
(11.15;
and then catalytically
to give [303](1,3)-ferrocenophane
The stereochemistry
ponding
with LiA1H4-AlC13
present
in the
of ferroceno-
rings were linked
via intramolecular
coupling
301
Cl
of the corresponding For example
reductive
Rl = CHO, R2 = H; derivatives
foray1 compounds
(11.19 and 11.20) respectively.
transannular
11.15
References
compounds
ferrocenophanes
have been prepared aldehydes.
p.
317
of the dialdehydes
R1 = 3, R2 = CHO) produced
of these and related Several
coupling
with a TiCl 4-Zn r'eagent.
including
by reductive
UV-visible electronic
were
examined
The structures by spectroscopy
the acetylenes
coupling
spectroscopy interactions
11.16
(11.18;
the biphenyl [ 1631.
(11.21 and 11.22)
of the corresponding
was used to investigate
11641.
11.17
11.18
11.19
11.20
11.21
The pentabridged ferrocenophanes (11.23 and 11.24) have been prepared from the propionic acid (11.25). The structures of the ferrocenophanes (11.23 and 11.24) were confirmed by X-ray analysis. The crystal and molecular structures of both compounds were almost identical and both contained a rotational disorder about the axis of five fold symmetry through the two Formylferrocene has been I-cyclopentadienyl rings [165]. condensed with the appropriate formylparacyclophane to give the cyclophane complex (11.26) and the diparacyclophane complex (11.27) has been obtained by complexation of the appropriate The reaction of tetrakis(triphenylligand with iron [1661. phosphine)palladium(O) with 1,2,+trithia[3]ferrocenophane The structure produced the heterobinuclear species (11.28). The ferrocene of this complex was determined by X-ray analysis.
303
11.23
11.22
CH2CH2C02H I
11.24
11.25
moiety was slightly bent and the geometry about the palladium atom was a distorted square plane [167]. Trithiaferrocenophane (11.29) has been treated with dodecacarbonyltriiron to form the dithiolatodiiron complex (11.30) [168]. l,l'-Ferrocenedithiol has been used to prepare the polythiaferrocenophanes [11.31, X = (CH2)2, (CH2)2 S(CH2)2, (CH~~~S(CH~~~~(CH~~~, n = 2,3; (cH2)3s(CH2)ns(CH2)3, The spectroscopic properties of these compounds n = 2, 33. The [5]ferrocenophane (11.32) has been were discussed [169]. obtained by treatment of ferrocene-l,l'-dithiol with pentaBridge reversal in the complex (11.32) erythritol tetrabromide. Diastereomeric has been examined by 1H NMR spectroscopy [170]. oxathiaferrocenophanes, for example the complex (11.33), have
11.26
11.27
Q-\
S
S
0
Fe
@d-
\
PPh3
o0
11.28
S
S
/
11.29
11.31
305
11.32
11.33
been prepared by reaction of 1,l '-bis(hydroxymethyl)ferrocene with dithiols containing ether linkages [171]. 1,2-Bis(hydroxy-
CH20H
Q 0
Fe
Referencerp.317
306
11.40
11.39
11.38
methyl)ferrocene (11.34) has been attacked by hydrogen sulphide to form the dithiaferrocenophanes (11.35 and 11.36) [172], The cleavage of the [l]-ferrocenophane (11.37) &th phenyllithium produced 1-lithio-1 I-diphenylphosphinoferrocene which was coupled with acetyl chloride to produce the heteroReduction of this annularly substituted acetylferrocene (11.38). ketone produced the corresponding alcohol and attempts were made to convert this to the amine (11.39), but the yields were An alternative synthetic route to the amine (11.39) small. The ferrocenophane (11.40) was treated with was devised.
Li
R1
Fe
11.41
11.42
307
phenyllithium at low temperatures and on hydrolysis the amine (11.39) was produced in good yield [173]. Treatment of the l,li-dilithioferrocenes r11.41; R1 = H, CHMeNMe2, CH(CHMe2)NMe2] with RzMC12(PhPC12, PhAsI2, Me3CPC12) produced the corresponding The crystal structures of these [llferrocenophanes (11.42). The mean tilt of the 7-C5H5 rings compounds were determined. in the phosphorus bridged compounds was 27.0' and for thezsenic derivatives 22.9' [174]. 12. FERROCHNE-CONTAINING POLYMERS Radical polymerization of l,l'-divinylferrocene (12.1) gave a homopolymer which was shown by 13C NMR and Moessbauer spectroscopy to be a cyclopolymer containing a three-carbon bridged ferrocene unit. When cationic polymerization was used then the polymer had an acyclic structure [175]. Divinylbenzene and vinylferrocene have been copolymerized at 680'~ and 125 MPa and the resulting copolymer was subjected to pressure pyrolysis to give carbon containing finely dispersed iron. The pyrolysis conditi.onsused determined the morphology of the carbons which consisted of fibrils, spheresand polyhedra [176]. The rate of intramolecular electron exchange between pendant ferrocenyl groups in poly(vinylferrocene) has been determined by an NMR The rate constant was determined line broadening technique.
9” 0
Pe
Refemllceep.917
Fe
308
Electroactive
as 6.4 x 10*[177]. ferrocene
(PPVF) films have been deposited
electrodes
for use in electrochemical
scopic and ellipsometric PPVF film surface demonstrated
were
studies.
independent
in the
oxidized
to
charge-potential
to the square
of the solvent in the presence
trifluoride molecular
etherate
weight
the polymer
Adducts electron
measurements
of ferrocene
underwent
cationic
of trifluoroacetic
of 8100-14700.
ethylene
material
the monomers
R1R2C=CH2
R2 = m-carbonyl,
and
conductivities (H,C=CRl),Z
1 R-
12.3
in and
was also present with
and tetracyanosusceptibilities
oxidation
of iron(I1)
and to
of the adducts were and polymerization
of
(R1 = ferrocenyl,
Z = 1,7-m-carboranediyl)
PPh
unsaturation
2,2'-(2,5-cyclo-
The magnetic partial
The preparation
high [180].
average
poly(l,l'-ferrocenylene)
such as iodine,
indicated
The electrical
iron(II1). relatively
acid or boron
Some residual
Fe(II)-Fe(III),
have been prepared. spectra
homopoly-
by 'H and l3 C NMR spectroscopy
of crystalline acceptors
and were
used [178].
hexadiene-1,4-diylidene)bispropanedinitrile Moessbauer
and ferrocenium
of their concentrations
to give a polymer with a number
was identified
some mixed valence,
spectro-
residues
l,ll-Diisopropenylferrocene merization
carbon
photoelectron
Ferrocene
that the activities
were proportional
on glassy
X-ray
vinyl-
foundto be appreciably
Equilibrium
ferrocenium.
c1791. various
plasma polymerized
have been investigated.
309
Treatment
of acetylferrocene
dehydration,
produced
of this monomer Products
oligomeric
products
between
underwent
in the presence
DTA at temperatures
(12.2).
were
were
and
evaluated
from the polymeric
in which
similar
catalysts.
Catalysts
The photochemical
complexes
Rl = H, R2 = OH)
A mechanism
characteristics
of this
[ 1841.
determined
and Photosensitizers
system
investigated.
dark reactions
in polymer
was proposed
ferrocene
of offset
composition [ 1861.
sensitivity
printing
has been prepared
or tri-t-butylferrocene
with
A similar
carbon
ferrocenes
[ 1871.
ferrocene,
dibenzylaniline
gave different wavelengths
good contrast or a mixture
[ 1881.
and relatively
They contained
a mixture
of mono-,
has
A light
from triethylferrocene and a toning
with high light
composition on exposure
Light sensitive
on polymethyl-
containing in a polystyrene to light of compositions
with
low cost have been developed.
of mono-,
di- and tri-t-butylferrocene
di-, tri- and tetra-isopropylferrocene
with tetrabromomethane
Fkferencesp.317
[l85].
plates
and tetrabromomethane
photoproducts
system
region was based
A light sensitive
system were
film which was suitable
tetrabromide
composition
in the long wavelength
have been
and the sensitometric
The ferrocene-tetrabromomethane
for the preparation sensitive
of the
layers
based photoimaging
been used as the basis of a photoimaging
together
and selectivity
Cobalt
(12.3;
and subsequent
ferrocene-tetrabromomethane
different
The
for the hydroformylation
reactivity
phosphines
the phosphine
OF FERROCENE
(i) Ferrocene
binder
R1 = H,
weight
13. APPLICATIONS
compound
(12.3;
and
The
8,900-161,000 amu showed catalytic that was molecular weight dependent [183-J.
with molecular activity
[182].
when appropriate.
as catalysts
to cobalt-triphenylphosphine formed
oligomers
and
The
by thermogravimetry
tridentate
they exhibited
of 1-hexene,
to Me2Si(CECH)2 catalyst.
in oxygen
to form complexes
chelating
were
and
R1 = Ph2P, R2 = Ph, n = 1, 2) combined with
octacarbonyldicobalt complexes
addition
characterized
l,ll-ferrocenylenephenylphosphine
ligands
by
ferrocenyllithium
of an H2PtC16
of up to 1000°C
R2 = Ph, n = l-4;
followed
The polymerization
[18l].
was also studied
from the reaction
methylphenylchlorosilane Ph2Si(CWH)2
with Li(SiPh2)4Li,
the monomer
and a toning
compound
[189].
310
In a related patent the composition contained methyl, ethyl or propyl acetylferrocenecarboxylate as the metallocene component. Low temperatures for development and short development times were claimed [190]. Ferrocenyldiphenylamine, diferrocenylphenylamine and triferrocenylamine (13.1; n = 1, 2, 3) respectively, have been dissolved in polystyrene or a polycarbonate and used to form electrophotographic layer materials with photoconductor properties [191]. Condensation polymers, such as poly(oxy-2,6-dimethyl-1,4-phenylene), have been solubilized by treatment with Cs salts, such as the Cs salt of ferrocene carboxylic acid.
\ & C02H
Fe
RPh3_n
Q-
PPh2
0
Fe
0
n
PPh2
Cl
13.2
CH~NM~~ 13.3
Irradiation at 435nm of the solubilized polymer films in the presence of dibromotetrachloroethane caused rapid darkening consistent with cation formation [192]. Asymmetric hydrogenation of the tetra-substituted olefinic acids R1R2C=CR3C02H (R1 = R2 = Me, R1R2 = CH2CH2, R3 = aryl) has been achieved with a catalyst system containing a coordination complex of rhodium, ruthenium or iridium and a chiral ferrocenyl-, ruthenocenyl-, osmocenyl- or For example, the olefin (13.2) pyrrolidinyl-phosphine ligand. was asymmetrically hydrogenated at 700 p.s.i. and 80'~ using a catalyst system containing [(7-norbornadiene)RhC1]2, the chiral ferrocenylphosphine (R,S)-(13.3), silver tetrafluoroborate and triethylamine [193]. A catalyst has been prepared, for use in the synthesis of ammonia, by the adsorption of potassium vapour and ferrocene The catalyst had much higher activity at on active carbon.
311
lower temperatures than a conventional iron catalyst. A linear correlation was observed between the ferrocene concentration and the activity increase. A Moessbauer study indicated the presence of ferromagnetic FejC and o&Fe with the at-Fe being the active centre [194]. 1-Benzoyl-1' -o-chlorobenzoylferrocene has been used as an intermediate in the preparation of l'-benzylferrocenecarbinol which was converted to the tricarbonylchromium complex and evaluated as a catalyst [195]. (ii) F errocene Stabilizers and Improvers Several ferrocene derivatives have been tested for their ability to prevent the ultraviolet induced aging of corrosion-protective films of low-pressure polyethylene on steel. The addition of acetyl-l,ll-diethylferrocene oxime to the polymer gave maximum resistance to ultraviolet aging and maximum protection of the steel from atmospheric corrosion [196]. A study has been carried out on the relaxation of stresses in modified polyethylenes. The mechanical properties of the polymer were improved by the addition of ferrocene [197]. Ferrocene has been used in the treatment of polyethylene and polypropylene wastes which were subsequently recovered [198]. The effect of ferrocene derivatives and cymantrene on the heat and radiation resistance of silicone rubbers has been investigated. o(-Methyl-@&dicyanovinylferrocene, l,l~-tetramethylsiloxanylferrocenophane and cymantrene increased.the heat and radiation resistance with the ferrocenophane being the most effective [lgg]. The incorporation of the ferrocenylamine thiocyanates (13.4; R = H, Me) into neoprene rubber produced vulcanizates with increased strength [200]. A small proportion of ferrocene or acetylferrocene and benzenesulphonic acid has been mixed with a formaldehyde-furfural-phenol copolymer and acetone to give a composition suitable for the treatment of wood. Samples modified in this way showed a loss in compressive strength and a low mass loss on accelerated aging [201]. Ferrocene or acetylferrocene, 0.5-1.5"/0, has been added to the same copolymer which was then used to retard the aging of wood [202]. A related patent described the modification of woudby the incorporation of the same copolymer containing a small proportion of benzenesulphonic acid and ferrocene to give a fracture-resistant
Reference8p.317
312
HRNHJ+ SCN-
Fe
6 0
13.4
material
[
2031.
derivatives
The addition
rate of emulsification A stabilizer
[204]. developed
[205].
-paraffin oil. readily
together
The results
by the alcohols
ferrocene
plasticizer
heated substrate
were discussed
the presence
(iii) Ferrocene Vanadium 2.12% vanadium
materials
in terms of the [206].
formed
Metallocene
copolymer,
with a
for electrophotography
atmosphere,
depositing
The gas carburization
[207].
vapour
speeded
the film on a
it in a reducing of steel products up the process
in
at a
[209]. in Analysis
has been determined by amperometric titration
with
in steels
titration
and iron were determined
potentiometric
in
thin films have been formed by evaporating
of ferrocene
lower temperature
and eight
additives
ions that were
and then heat treating
[208].
salt and
have been used to form the basis of
in an oxidizing
atmosphere
as antiwear
and the sulphides
transport
"$-Hematite magnetic ferrocene
with a combustible magnesium
such as styrene-vinylferrocene
charge-carrier
has been
of ferrocenyl-alcohols
have been tested
the
the mixture
emulsions
an oil soluble
of the ferrocenyl-carbenium
copolymers,
Vanadium
ferrocene
A series
ferrocenyl-sulphides
reduced
when air was blown through
benzyl alcohol,
a surfactant
oil mixtures
for fuel oil-water
that contained
emulsifier,
stability
of 0.05 wt.% of ferrocene
to 1:l water-lubricating
containing
with
ferrocene.
in nickel-based
ferrocene
O-14-
alloys
in 5-6M sulphuric
by acid.
313 Strong oxidizing agents such as chromium(V1) and manganese(VI1) interfered but large excesses of iron(III), molybdenum(V1) and relative to the vanadium(V) concentrations, did not copper( The concentrations of vanadium(IV) and interfere [210]. vanadium(V) present together in vanadium catalysts have been determined by a titrimetric method using a solution of ferrocene in propanol. Initially the vanadium(V) was determined amperometrically orpotentiometrically in a 5-6M sulphuric acid solution. After the addition of phosphoric acid the vanadium (IV) was determined by continuing the titration [211]. Iron(II1) and vanadium(IV) were determined in the presence of each other by amperometric or potentiometric titration with O.OlM ferrocene. Methods were developed for determining iron and vanadium in different alloys [212]. Ferrocenometric techniques have been used for the determination of standard reference materials [213]. Ferrocene has been proposed as a primary iron standard in volumetric analysis since it may be purified easily, it is resistant to oxidation and it is not hygroscopic [2l4]. Ferrocene has been determined by potentiometric titration with iron(II1) chloride in methanol containing perchloric acid [2l5]. Gold(II1) has been determined by potentiometric titration with a O.OlM ferrocene solution. Copper and a four fold excess of Ferrocene has been used as a silver did not interfere [216]. reducing agent for palladium(I1) and silver(I) in aqueous-organic solutions. A gravimetric procedure, using ferrocene, has been developed for the determination of these elements in palladium-silver alloys [217]. A ferrocene-modified platinum electrode has been used as a potentiometric sensor for &-ascorbic acid in an aqueous glycine buffer at pH 2.2. In recovery experiments with pure &-ascorbic acid the relative standard deviation was l.y/oand in the analysis of fresh orange juice the relative standard deviation was 6.1% A kinetic investigation of the oxidation of NADH by [218]; ferrocenium salts has provided an estimate of the Eat value (1.05 V vs. NHE) for the one-electron no proton couple NADH/NADHt [219]. (iv) Combustion Control The addition of metallocenes and related,compounds was
Referenceap.317
314
effective in reducing the smoke and hydrogen chloride evolved in the thermal degradation of poly(viny1 chloride). Nickelocene and dicyclopentadienyltitanium dichloride were more efficient in smoke suppression than ferrocene [220]. The combustion velocity of ammonium perchlorate based solid propellants for rocket igniters has been improved by using dibutylferrocene as a catalyst in place of Fe203 [221]. The use of diesel fuel containing 20-30 ppm of ferrocene was effective in replacing carbon deposits with catalytic iron oxide on the combustion surfaces of diesel engines. Subsequent operation with a lower concentration of ferrocene, 10-Q ppm maintained the iron oxide layer [222]. (v) Biochemical and Biological Applications The toxicity of the ferrocene hematinic (13.5) and its effects on the liver and adrenal cortex of the dog, rat and The hematinic (13.5) was monkey have been investigated. administered orally at dosages ranging from 0 to 500mg/kg/day to dogs, for two weeks, and to monkeys and rats, for six weeks. High-dose rats had distended abdomens due to enlarged livers while high-dose dogs and monkeys exhibited the following signs: emesis, depression, ataxia, anorexia and a high number of deaths [223]. The effect of the ferrocenyl group on the antimicrobial activity of (J-lactamic antibiotics has been investigated and the reaction conditions determined for the preparation of l,l'-ferrocenyldicarboxamidopenicillanic acid (13.6) and l,lf-ferrocenyldicarboxamidocephalosporanic acids (13.7; R = The ferrocene analogues of the CH20COMe, CH2S.CN2CS.Me) [224].
Q-i 0
Fe
S
13.5
315
C02H
b,
CONH
0
S
TT N
0
C02H
C02Na
13.7
13.6
antiinflammatory agents tolmetin, fenbufen, flurbiprofen and fenclofenac have been prepared and tested for biological The compounds exhibited little or no antiarthritic activity. or platelet antiaggregatory activity [225]. Analogues of enkephalin, substance P(SP) and bradykinin containing ferrocenylalanine, cymantrenylalanine and-tricarbonyl!7-cyclobutadiene)ironalanine have been prepared by solid-phase synthesis. The properties of these molecules were compared with those of the corresponding phenyl containing derivatives [226].
Q-
C02H
NPh
0
Fe
0
J5
13.8
Fe
316
Fe
13.10
Biologically
active
by treatment with
peptides
of the peptide,
ferrocenecarboxylic
followed
by cleavage
have been labelled
acid
(13.8) or cymantreneacetic
with HF-anisole
such as E-succinamidophenobarbital, ferrocenylmethylamine
have been combined with
and used to obtain antibodies
Ferrocenylmethanol eleven nitrogen
and +ferrocenylethanol
containing
and the ferrocenylimine
of HBF
to give a series
compounds
4
had bactericidal
Staphylococcus derivatives
and Candida
containing
species
Sphaerotheca
pyrethroids
(13.10;
@H2.C6H4SCBMe)
The products
fullginea
X = CH2CH2,
(+)-trans-chrysanthemic
activity
[229].
These
against
A number
of ferrocene substituents
For example,
benzoylferrocene
on cucumbers
[230].
CH2CH=CH,
have been obtained
propanecarboxylic
(13.9) in the presence
aryl, acyl and carboxyl
have been tested as fungicides. controlled
triphenylphosphine,
of onium compounds.
and fungicidal
alkyl,
have been treated
heterocycles,
dialkylsulphides
4
for
[228].
metalloimmunoassay
or HClO
acid
Drug derivatives,
[227].
to form haptens which were in turn treated
with bovine serum albumin
with
with metallocenes
bound to a solid phase substrate,
Ferrocenyl-
CH2CH2SCH2,
by the esterification
of
and (+)-2,2-dichloro-l-methylcyclo-
acids with the appropriate
(13.10) showed
insecticidal
ferrocenylalcohols.
activity
against
house-
flies [231-J. The E-nitrophenyl (13.11;
ester of (E)-ruthenoceneacrylic
M = Ru) was shown to react
p-cyclodextrin,
but with a poorer
in a complex
binding
acid
to acylate
and rate constant
than
e
/
0 M
6
0
0
qfC0~~N02
0
0
Fe
6 0
0 *02
13.12
13.11
13.13
for the corresponding The cyclopentenyl an excellent
ferrocene
ester
substrate
The effect of pressure E-nitrophenylesters P-cyclodextrin
compound
(13.11;
(13.12) was prepared for the cyclodextrin on rates
and found to be reaction
of transacylation
(13.11 and 13.13)
was also investigated
M = Fe). [232].
of the
in the presence
of
[233].
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FERROCENE ANNUAL
SURVEY
COVERING
BERNARD W. ROCKETT Department
and GEORGE MARR
of Physical
Wolverhampton,
THE YEAR 1983"
Sciences,
The Polytechnic
WV1 1LY (Great Britain)
CONTENTS 1.
Reviews
255
2. Structural
determinations
Theoretical
3. 4. 5. 6.
256
studies
Spectroscopic
and physico-chemical
Electrochemistry Preparations
10. Ferrocene
studies
and photosensitive
267
electrodes
272
of ferrocene
7. Reactions of ferrocene 8. Ferrocenium salts and mixed-valence 9. Ferrocenyl
259 259
carbenium
273 274
salts
277
ions
278
chemistry
(i) Derivatives (ii) General
containing
(metalloids)
ferrocenophanes
12. Ferrocene-containing
and annelated
ferrocenes
polymers
catalysts
307
stabilizers
(iii) Ferrocene
in analysis
(v) Biochemical
309
and photosensitizers
(ii) Ferrocene (iv) Combustion
296 309
of ferrocene
(i) Ferrocene
278 288
chemistry
11. Biferrocenes,
13. Applications
other metals
311
and improvers
312 313
control and biological
314
applications
14. References
317
1. REVIEWS Kauffman discovery
and aromatic stabilized
Cd
l
has recorded
of ferrocene character
+ Annual
Survey
Chem.,257
Referencesp.317
[l].
carbocations
The chemistry
the events
The chemistry
has been the subject
of chelate
covering
(1983) 209
that led to the
and the con'firmation of its structure
complexes
of ferrocenyl of a brief review
containing
organo-
the year 1982 see J. Organometal.
256
metallic
ligands with arene
has been surveyed
by Rybinskaya
organometallic
derivatives
2. STRUCTURAL
DETERMINATIONS
X-ray analysis ferrocene through clinic
was carried
temperature
of workers
face-centred
of 164K.
consisted
by X-ray diffraction The crystal
of ferrocene
and lattice
and molecular
Vinylferrocene
of molecular
The same group energy
structure
(2,l) has been determined
[7].
cooled
from room
structure
calculations
crystallography
crystal
When the tri-
[5].
the disordered
of the
by X-ray
has been attacked
(3-iodopentane-2,4-dionato)cobalt(III)
[4].
phase of
of a mixture
at room temperature dicyanovinylferrocene
The
triclinic
and 21 symmetry
investigated [6].
[3].
by cooling a crystal
its structure
groups
have been reviewed
out at 130K on a single
phase was obtained
packings,
and Krivykh
of ferrocene
of the metastable
the transition
temperature
and cyclopentadienyl
in the presence
by trisof
COMe
(W2
CMe=C
Fe
Fe
6
6 0
0
2.2
.2.1
triphenylphosphine ferrocenyl
and palladium(I1)
dihydrofurans
and 2.3) were mechanism
by which
structure
of the helical
X-ray
analysis. the two
they were
by X-ray
The compounds
crystallography
formed was discussed
ferrocene
This structure -cyclopentadienyl
7
to form the two isomeric
(2.2 and 2.3).
characterized
where
2.3
(2.2
and the
[8].
The
(2.4) has been determined
represents
by
the first ferrocene
rings are linked by unbroken
257
2.4 conjugation [y]. The crystal and molecular structure of benzyldiphenylferrocenylphosphonium chloride has been determined by X-ray The results indicated that it was possible for the analysis. filled hag molecular orbital of the ferrocenyl group to overlap with an empty 3d orbital of phosphorus. The implications of this overlap on the rates and stereochemistry of the Wittig reactions of (carbomethoxymethylene)diphenylferrocenyl- and (carbomethoxymethylene)diferrocenylphenyl-phosphorane with The structure of the benzaldehyde were considered [lo]. ferrocenylphosphine-rhodium complex (2.5; R = CMe3) has been determined by X-ray analysis. The rhodium atom was shown to be in a distorted square planar environment. The behaviour of the complexes (2.5, R = CMe3, Ph) as homogeneous catalysts in the hydrogenation of CH2=CRC02H, where R = NHCOCH , CH2CO2H, and PhCH=CRC02H, where R = NHCOCH3, Me, was investigzted [ll]. The crystal structure of the ferrocenyl quaternary ammonium salt c (7-CgH5)Fe(C5H4CHZNMe3)];1B10H10 has been determined by X-ray analysis [12]. The crystal and molecular structure of (ferrocenylmethyl)(l-cyclopentadienyl)dicarbonyliron has been determined by X-ray methods [13]. The crystal and molecular structure of the ferrocene (v-cyclopentadienyl)iron complex (2.6) and of three related complexes have been determined by X-ray crystallography [14]. Several methyl-substituted bis(7-pentadienyl)iron complexes, including the dimethyl derivative (2.7) have been prepared and
FLeferencesp.317
+ I6
258
L
Fe
7
“‘0;;
0
characterized molecular
as red air-stable
structure
crystallography.
eclipsed
ligand
a little greater properties
El51
conformation
The molecule
were similar
Fe Fe
2.7
adopted
with metal-carbon
l
301
and
(Z,7) has been determined
than those in ferrocene.
of the complexes
The crystal
compounds.
of one complex
by X-ray
2.6
a gauche-
bond distances
Physico-chemical to those of ferrocene
259
3.
THEORETICAL STUDIES
The effect of substituent groups and of ligand replacement on the frontier orbitals in ferrocene has been examined. Replacement of a cyclopentadienyl ligand by arene caused major changes in the el (antibonding) interaction which was decreased and in the back-bonding e2 (bondin&) interaction which was increased. The introduction of methyl substituents caused a minor increase in the el interaction and a minor decrease in the e2 interaction, The introduction of acetyl A force field study groups caused the opposite effect [16]. of ring orientation in ferrocene and ruthenocene has been Minima in the intermolecular strain energy carried out. corresponded to the observed conformations only if the relative orientation in all the neighbouring molecules was assumed to The bonding change with that of the reference molecule [17]. and reactivity of phosphaferrocene (3.1) and diphosphaferrocene have been studied by nonparametrized MO calculations. The ligands were shown to form Z-bonds with the metal 2 orbitals and the calculated electrondensity distribution in phosphaferrocene (3.1) was in accordance with the observed distribution. Charge control was important in determining the regioselective character of electrophilic substitution in phosphaferrocenes. Lone pair electrons associated with phosphorus were localized on that atom but did not confer nucleophilic properties on phosphorus since the lone pair was not in a frontier MO [~_a]. INDO-(crystal orbital)calculations have been used to obtain the energy band structure and density of electronic states in polyferrocenylene [lg]. 4.
SPECTROSCOPIC AND PHYSICO-CHEMICAL STUDIES
Intercalation compounds of ferrocene, lithium and pyridine derivatives in the layered transition metal oxyhalides MOX, where X = Cl, Br, M = V, Cr; X = Cl, M = Fe have been prepared and characterized by X-ray diffraction, voltamtnetric, Solutions of monosub'H NMR and Moessbauer methods [20]. stituted ferrocenes and biferrocene in freon mixtures have been The monocations produced subjected to y-irradiation at 78’~. from biferrocene and phenylferrocenes showed an absorption band that was assigned to electron transfer from ferrocenyl or phenyl
Referencesp.317
260
to the iron atom [21], ferrocene
tracer has been studied
The temperature probability splitting energies
Butylrubber
dependence
of resonance
and chemical
3d metallocenes determined
of the Moessbauer
parameters,
band widening,
shift, were determined unstable
negative
[22].
The of the
(4.1; M = V, Cr, Mn, Fe, Co, Ni) have been
by electron
scattering
assignment
quadrupole
ion states
transmission
spectroscopy.
(4.1; M = Fe, Co, Ni) calculations
complexes multiple
by \6-resonance spectroscopy.
absorption,
of the low-lying,
57Fe-enriched
containing
employing
XW method with stabilization
of the observed
metal 3d, 4elg orbital
states
to electron
or cyclopentadienylZ*
Q
Q-
6
6
the
permitted
capture
the
into the
orbitals
R
0
For the
[23].
CR1=NNHCOR2
0
F‘e
M
0
Fe
0
4.3
4.2
4.1
Open-shell, ferrocene, mission
vanadocene
metallocenes
The spectra
spectroscopy.
of multiple
scattering
and chromocene,
have been studied X&
and closed-shell,
by electron
were interpreted
calculations
[24].
copy has been used to investigate
the electronic zirconocene,
ferrocene.
The binding
were significantly groups
into a metallocene
reduction
energies
altered
The mass spectra
effects
hafnocene
of and
of the inner shell electrons
thus the introduction was equivalent
of the metallocene
by the use
ESCA spectros-
methylsubstitution
in titanocene,
trans-
of ten methyl
to a one-electron
[25].
of the substituted
R = COCH3, CH3, CHO, C02H, CH20H,
ferrocenes
COPh, CH2N(CH3)2]
t4.2; have been
261
reinvestigated making intensive use of the metastable ions. The observed primary fragmentations of the molecular ions were different in some respects from those previously suggested [26]. Acetyl- and benzoyl-ruthenocene and l,l'-diacetylruthenocene have been studied by mass spectrometry. The high metal-ligand bond strengths led to extensive fragmentation of the ligands by comparison with ferrocene [27]. The mass spectra of eight ferrocenyl aroylhydrazones (4.3; R1 = H, Me; R2 = Ph, substituted Ph, pyridyl) have been measured and interpreted in terms of skeletal and hydrogen rearrangements and bond cleavages The gas phase reactions of Fe+, Co+ and Ni+ with cyclic [28]. hydrocarbons have been investigated by Fourier transform mass spectrometry. The intermediate [Fe(C5H6)]+ cation combined readily with cyclopentane and underwent multiple dehydrogenations to give the ferrocenium cation [(C5H,-)2Fe]+[29]. Zagorevskii and co-workers have reported a correlation between mass spectra data and -endo-exo-stereoisomerism in the rhodium complexes R = ferrocenyl, methyl and 4.5; exo-isomers shown) (4.4; [301
l
&j----Hb&m__ OH
R \ 0
H
9 ’ ‘_.*’
Me& 4.4
e 4.5
Photoionization efficiency curves have been recorded for ferrocene vapour between 1900.and 590 8. The parent ion had an appearance potential of 6.747 eV and the [(7-C5H5)2Fe]+ fragments [(v-C5H5)Fe]+ and Fe+ appeared at 13.162 and 13.506 Ferrocene and bis(q-arene)chromium eV respectively [31]. complexes have been ionized on a tungsten oxide surface.
Fleferencesp.317
Ferrocene
formed a molecular
observed.
The ion current
approximately
ion but no fragment increased
1150K the coefficient
ions were
with temperature
of surface
and at
ionization
was
8 x 1O-3 [32]. A Moessbauer been carried liquid
crystals
dissolved
study of anisotropic
over the temperature
range
and reappeared
Au- and 57Fe-Moessbauer ferrocenyl-gold presence
complex
Au(PPh3)2
of cyano biphenyls
80-300K.
spectra
(4.6).
effect
was changed
have been recorded [34].
BF -
4
with the
A series
-
+e
[33].
for the
Q-Q
+
Fe
or
The data was consistent
in the complex
has
in
and terphenyls
The Moessbauer
as the temperature
of Au(I) and Fe(I1)
6
diffusion
dissolved
of i-methoxybenzylidene-~-butylaniline
in a eutectic mixture
c@appeared
molecular
out with l,l'-diacetylferrocene
of
+
Fe
0
4.6
l,l'-diacetylferrocene
complexes
SnCl 4, FeC13 and TiC14
has been studied
of the Lewis acids AlC13, by Moessbauer
All the complexes exhibited a lowering COPY. splitting relative to the uncomplexed ligand. in quadrupole chemistry polymers
sp'litting were discussed
of the complexes
[35].
based on vinylferrocene
Moessbauer copolymer
spectroscopy. exhibited
fraction
between
motional
narrowing.
anharmonic
A Moessbauer
The decreases properties
have been investigated
of
by
Acrylonitrile-vinylferrocene
an anomalous The results motion
of quadrupole
in terms of the stereo-
The dynamic
decrease
80 and 130K accompanied
hindered
spectros-
of the recoil-free by line broadening
were interpreted
of the ferrocenyl
and electrochemical
and
in terms of
group [36].
study has been carried
out on
263
(4.7; X = Cl, Br, I). The Moessbauer (4.7; X = Br, I) indicated average valence states for the iron atoms but the cation (4.7; X = Cl) the haloferrocenes spectra
showed
of the cations
a trapped
difference
was
valence
state
for the iron atoms.
found in the half-wave
potentials
No
of these
[371.
molecules
The 57 Fe Moessbauer
spectra
and &cyclodextrin
derivative-x-
-od-cyclodextrin clathrate which
collapsed
terms of reorientation of Gcyclodextrin
of ferrocene have been recorded
of the formylferrocene-
consisted
of a doublet
at low temp-
on heating
to a singlet
of reduced
This variation
intensity.
clathrates
the spectrum
For example,
at 78-320K. eratures
of a series
in the spectrum
was interpreted
of the formylferrocene
as the temperature
in
in the cavity
increased
Moessbauer
[38].
spectroscopy
has been used to study oxidation
interaction
irreversible
phase transitions
of ferrocenium
ion-iron
oxychloride
between
intercalates
of the type [(7-C5H5)2Fe]+
with 57 Fe labelled
[(6-7FeOCl)]the unstable
dynamic
ferrocenes.
e-e[Fe2+
At low temperatures
Eq. 4.1 and Eq. 4.2 in the
equilibria,
Ferrocene#[Ferrocenium]+ Fe3+OCf+
layers
and
+ e-
para OCl]-
Eq. 4.1 or [Fe2+ antiferro
OCl]-
Eq. 4.2 guest and host layers respectively phase
transitions
[39].
The 57 Fe chemical sensitive
indicator
shown by high anisotropy, anistropy determined
shift in ferrocenes
of ring tilting
field shifts
the electric of ferrocene
bonding
quadrupole
moment
resulted
axes.
in directions
It was indicated
in transfer
constants
was found
chemical
have been
have been used to show that
of electronic
rings
[41].
parallel
that metalcharge
from
The 13C and
(4.8;
of the benzylideneferrocenophanediones
carbon
being
and the magnetic
R1 = H, Cl, Br, NMe2, OMe, Me, N02, CN, R2 = H; R2 = Cl, Br) have been recorded and interpreted. of the carbonyl
tilting
polarization
in cyclohexane
were more polarizable
the metal to the cyclopentadienyl 'H NMR spectra
with increased
and ruthenocene
to the ligand-metal-ligand
has been used as a
The effective
[40].
The results
at 25'C.
these metallocenes -1igand
gave rise to irreversible
R1 = H, A correlation
shift with the Hammett
for both z- and E-CO groups
[42].
Electron
264
Fe
4.8
4.9
P-cocH=c Fe
Fe
ti
0 4.11
4.10
density
distributions
(4.9, 4.10, 4.11; using
in the phenyl-ring
effects
of substituents
and
13C N?iR spectroscopy.
on electron
The 57 Fe NMR spectra with natural
of
was
28 mono- and di-substituted 57Fe have been recorded using
reference.
on the high-frequency
shielding
effect of substituents
was shown
to be important
carried
distributions
abundance
as an internal
were mainly
A complete
density
The
[43].
ferrocenes ferrocene
ferrocenes
X = H, ;-CHO, 2 -0Me) have been measured
cyclic voltammetry
discussed
substituted
molecular
was discussed
in determining
dynamics
out in E-xylene
The resonances
observed
side of the reference.
study
and ring
57Fe shifts
of acetylferrocene
by dielectric
relaxation
The tilting
[44). has been
measurements
265 at 100 MHz-38
GHz and 293-323K
intermolecular
association
observed
between
molecule
exhibited
the solute
axis perpendicular
Ii451 -
around
the molecular rings or to
reorientation.
Similar
found between constants
An attempt residence motion
showed
neutron
the different
techniques
were
rings
considered
of ferrocene radical
to
formed within
give
Electrodes cations
reversible
between
kinetic
ferrocene
that anionic non-ionic
micelles
The intermediate the reaction
in the presence
by picosecond
oxidation
absorption
and decayed
of the diphenylmethyl
and the diphenylmethyl
cation
inhibit
the transfer
the process
and T~(OAC)~
has been
the
in ivater [50].
while
[sl].
cationic
and
The reaction
of a kinetic
species
study.
was hydrolysed
to give the observed
conditions
reaction
has shown
to form 1-ferrocenyl-1,
the subject
methoxythallation
conditionsused
[kg].
and octyl-ferrocenium
and used to determine
and octyl-ferrocene
catalyze
Under the same reaction
Referencesp.317
[48].
study of the electron-transfer
vinylferrocene
2-dimethoxyethane
when the three
and {Co(l,10-phenanthroline)]3+
micelles
energies,
ion and the diphenylmethyl
to dipropyl-
of dipropyl-
A stopped-flow
between
ferrocene
phase
of activation
35~s of the photolysis
have been constructed
solubilities
order-disorder
studied
at the same rate by ferrocenium radical
and calorimetry.
has been photolysed
The ferrocenium
were
of metallocenes,
of the solid state reorientational
together
and the reaction
spectroscopy.
and X+(R)
could only be derived
Diphenylchloromethane
was
by vibrational
scattering
that the determination
times and geometries
of aromatic
On application
A series
has been studied
quasielastic
to classify
transitions
[47].
vibrations
correlation
of C=O vibration
fragments
ferrocene,
a linear
were
The effect
valence
has been investigated.
the wavenumbers
included
of carbonyl
equation
and l,l'-
obtained
[46].
for acetylferrocene
Duyse
of structural
spectroscopy,
was observed
The results
on the wavenumbers
derivatives
behaviour
were made on benzoyl-
in E-xylene.
of the Seth-Paul-Van
which
Debye-like
to those observed
in ferrocene
to rotation
measurements
of substituents
The acetylferrocene band in the GHz-region
to the two q-cyclopentadienyl
-dibenzoyl-ferrocene similar
either
No
of any type was
molecules.
one sharp absorption
and this was assigned molecular
at low concentratians.
or interation
under
product.
P-methylvinylferroce
gave
266
both addition
and substitution
The effect of ferrocene substituted centration
trans-stilbenes
products
[52].
on the photoisomerization has been investigated.
of The con-
of the cis-isomer formed at equilibrium in the
photoisomerization of the trans-isomer (4.12; Rl = MeO, R2 = N02) was decreased by the presence of ferrocene. This was taken to indicate the participation of a triplet state, Ferrocene had no effect on the photoisomerization of the trans-stilbenes [4.12; R1 = NMe2, R2 = P(0)Ph2, Br] [53]. The R2
vapour pressures of benzoyl- and l,l'-dibenzoyl-ferrocene have been measured by a torsion-effusion technique. The pressure-temperature equations were derived and second-law treatment of the data produced the heats of sublimation [54]. When single crystals of ferrocene were cooled below the X-type phase transition at 163.9K, crystal disintegration occurred with explosive violence. The strain energy released at the disintegration was 1.10 kJmol-1. The disintegration was explained in terms of an energy transfer from the strain energy accumulated in the domain boundaries in a form of elastic energy to the kinetic energy of disintegrated crystallites [55]. The phase transitions of ferrocene-d10 have been examined. The high-temperature phase was easily undercooled to give a A-type transition at 164.1~ in the metastable state. The stable low-temperature phase was obtained by annealing the undercooled A first-order phase transhigh-temperature phase at 190K. ition occurred between the stable low-temperature and highA new low-temperature temperature phases at 25lK [56]. crystalline phase of azaferrocene stable at <28x has been found from the measurements of proton spin-lattice relaxation
267
time and differential 5.
ELECTROCHEMISTRY The operation
with polymer ferrocenes
thermal
AND PHOTOSENSITIVE of electrodes
ELECTRODES
chemically
films has been the subject
were among
neopolarographic polymerized
[57].
analysis
chemically
modified
Small band gap semiconductor electrodes, L-591 * and In203 glass electrodes, have been chemically the surface-active
redox
couple
electrodes to anchor
carboxylic
the active n-Type
way [60].
and l.OM lithium
ferrocene
silicon
open-circuit
arsenide
The properties
and rotation
of two-layer
References p. 311
in aqueous
the Fe3+/Fe2+
and
in acetonitrile.
in
solutions
The values
from water
containing
and 0.22V [63].
to light.
wafer which was
polymer.
The polymer with
has been determined
(111) single-crystal
photoelectrochemical
and I/I- redox
The
has been carried
of poly(chloromethylstyrene) The stability
has
of the under
exposed
silicon
coated
of
The electrochemical
of ferrocene
crystal
ferrocene-polypyrrole
electrodes
containing
[64].
using n-type
photoelectrode
a semiconductor
single
by the treatment
a lithioferrocenophane
[Sl].
hexacyanoferrate(I1)
coated with a ferrocenophane was prepared
[62].
n-silicon
of hydrogen
out by using as the cathode The cathode was a R-type
of 10.1% A high
disc electrodes
and K4Fe(CN)6-NaC104
of potassium
generation
ion
were -examined as a function
velocity
by cyclic voltammetry.
in the presence
silicon
rotating
in
in this
with 0.2M
efficiences
with ferrocene
were 0.3lV in the presence
photoassisted
in methanol
serving
stability
into electricity.
silicon
of a gold modified
been examined potentials
Electrode
exhibited
perchlorate
ferrocene-Et4NC10q-C2H50H
of
l-hydroxyethylferrocenium
of the electrades
light intensity
complexes
cell has been constructed
or p-type
tetrabutylammonium
by
complex
of 0.53V was also achieved
An electrochemical
such as n-Si modified
cells was enhanced
electrodes
0.5mM
electrode
was used to modify
the chromium
group.
of sunlight
voltage
of chromium
Ferrocene
with
perchlorate
for the conversion
behaviour
acids.
photovoltaic
l-hydroxyethylferrocene,
gallium
properties
by this procedure
photoelectrochemical
Poly-
Cyclic
have been used to study a plasma-
vinylferrocene-film
using
by coating
of a review.
used [58].
the polymers
methods
modified
couples
cells
[65].
268 l,l'-Diformylferrocene poly(l,l'-ferrocenylene
(5.1) has been used to prepare
vinylene
phenylene
vinylene)
(PFVPV)
PFVPV was an insulating material with a high resistivity (5.2). but on oxidation (doping) with iodine, bromine or arsenic (V)
CHO
Fe
+
DMF
Ph3P=s-PPh3
CHO
5.1
n
fluoride
it became
a semiconductor with conductivities ranging -1 Iodine doped material underwent an .
from 10 -4 to 10-gRcm instantaneous
two-fold
increase
in conductivity
when illuminated
75W tungsten lamp [66]. Ferrocene monomers such as the unsaturated ketones (5.3; Y = Cl-Cl0 alkylene, carboxyl,
witn
a
alkylenoxy)
have been converted
to crosslinked
to form a gel in an electrolyte. was a semiconductor, illuminated
were immersed
to form a photovoltaic
polymers
Two electrodes,
in the electrolyte device
and used
one of which
[67, 681.
and The poor
269
Y-NHCOCH=CH2
Fe
Y-NHCOCH=CH2
5.3
charge
transfer
the oxidation couple
characteristics
and reduction
have been attributed
difficulty electrode
surface
electrodes
using
which
transport.
limited
[69].
carbon
by an argon
plasma.
were studied
charge
films the reactions (T-Me5C5)2M,
and their structures ring enhanced
and all the metallocenes nature
studies
where M = V,
investigated
verified
of the following
investigated.
its ligand were
low
the reversibility
process
where
M = Cr,
Mn, Fe, Co, Ni: (I-Me5C5)~M~[(7-Me5C5)2M1+ + eThe incorporation of an ionic dye (croconate poly(vinylpyridine)
coated
electrodes
significant
Ftefemncesp.817
were
[70].
Cyclic voltammetry
produced
electrooxidation
via
and the ferrocenium
of electrochemical
of the I-cyclopentadienyl
and one electron
on glassy
ferrocene
of decamethylmetallocenes
field strength spin.
of the
covered with a thin film
of thicker
Cr, Mn, Co, Ni, has been prepared Alkylation
This
previously
between
hindrance
In the presence
A series
for
derivatization
of the electrodes
On an electrode
without
used
instability.
polymerized
properties
the redox reaction
ion proceeded
electrodes
1,1' -ferrocenediyldichlorosilane
had been etched
cyclic voltammetry. of polymer
by chemical
has been plasma
The electrochemical
diffusion
to oxidative
has been overcome
Vinylferrocene
of nickel
of the ferrocene-ferrocenium
of soluble
polycrystalline changes
ferrocene
c711 violet)
into
tin (IV) oxide
in the kinetics
derivatives
[72].
of A
270 reversible
cyclic voltammogram
of ferrocene
for the one-electron
in 1,2_dimethoxyethane
conditions
that enabled
minutes.
The formal rate constant
the ferrocene
with
pentadienyl including
ligand
half-wave
that the ferrocene
potentials
iron through
0
anion
diferrocenyl
varied
compounds
n = 0, 1 and 5.5) have been the study using platinum
difference between
acetonitrile,
acetone, Iron-to
Several
(5.4;
of an electrochemical The
-1
10'1 ems
and one planar pentahapto-cyclo-
[73].
the ketones
voltammetry.
x 10e3 cm s-1 which which was
it was postulated
had one bent tetrahapto-
subject
anion to exist for several o/-
that of ferrocene
From these results
under
of the ferrocene
at -45'C was approximately+;;7
electrode
was compared
reduction
has been recorded
the first
by >4OmV
electrode
and second
in solvents
such as methanol,
dichloromethane
and nitromethaae.
space interaction
was not important
[74].
~cocH2CcH2)n~
e
6
6
0
0
5.4
The effect Moessbauer
of carbonyl
spectra
acetylferrocene, increased in ketone ethylene spectra
group O(to
the oxidation
approximately
(5.7) reached
of the ketoferrocenes
charge-transfer
and the ketones
The results
were smaller
of ferrocene
ring
indicated
group through
splittings
shifts were approximately kinetics
(5.6
effect of the carbonyl
the ferrocenyl
The quadrupole
and
in formylferrocene,
the I-cyclopentadienyl
potential.
5O‘j“j' of the inductive
moiety.
but the isomer
on the redox potentials
ferrocenylphenylketone
A carbonyl
and 5.7).
groups
has been investigated
that group
the
in the Moessbauer
than that of ferrocene
the same [75].
at platinum
The
and vitreous
271
CH=CHCOPh
COCH=CHPh
Fe
Fe
5.6
carbon
5.7
electrodes
have been determined
chronocoulometry. of the electrode LiC104,
and solubility
quaternary cyanide
and of the supporting
Et,+NC104 or Et4NBF4
diffusion
ammonium
[ 763.
salts
melt electrolytes.
chloride
ion attack
occurred.
In acid melts, an intramolecular centre
carbon
electron
[77].
heterogeneous -crystal solvent
of the hole [79]. water
nucleophilic
ferrocenecarboxylic
(vinyl ferrocene)
between
[78].
potential increase
(5.8)
passed during
R.eferencee p. 817
through
on
acid
It was and
The rate of
a laser-excited
single-
and ferrocene in a non-aqueous -1 as a first-order constant
at 10 4 s
The contact
The dynamic
and
in p-cyclodextrin
angle
has been measured
in the form of a drop of O.lM potassiumchloride
electrode.
products
from the carbenium
has been investigated.
zinc oxide electrode has been determined
methyl
The effect of B-cyclodextrin between
in the cavity
hole transfer
in water,
salts decomposed
transfer
could be included
the iron atom was located
ferrocenylalkyl
ion charge-transfer
the quaternary
electrodes
that the acid
of several
In the basic melts
the rate of electron-transfer concluded
which was
alumini.um chloride-l-butylpyridinium
of ferrocenium
underwent
ion to the metal
electrolyte
have been investigated
chloride
step
were independent
Oxidation-reduction,
properties
and room-temperature
and glassy
by potential
The formal rate constants
as a film on the surface contact
angle decreased
the ferrocene
the reduction
wave
[8O].
oxidation
between
and poly-
of a platinum as the electrode wave but did not
272
n
Fe
5.8
6.
PREPARATIONS
OF FERROCENE
An improved been reported.
method
A catalytic
(2 mmol) was dissolved hydroxide
(15g) iron
(II) chloride
of these alkynes, Structural
and propyne
they were substituted with
-methoxyferrocene
(6.1).
proceeded
The helicene
[82].
cyclopentadienide
indicated
that
of (&
g>-
1,3-diphenyl-2-
that this reaction
to the differences
on indene and fluorene
which was
of the pentamethyl-
and is appreciably ion.
inchemistry
metal
to the helical
dianion
The basicity
ing (I-pentamethylcyclopentadienyl)
in a 13-step
and converted
ion has been determined
(q-cyclopentadienyl>transi.tion
All
(6.2) [83].
than that of the cyclopentadienide
has been related
61%) [81-j. 3-hexyne,
The reaction produced
(2.4) by way of the corresponding [841.
was
iron complexes.
(6.3) has been synthesized
treated with FeC12.2THF
methylation
2-pentyne,
It was postulated
from 2,7-dibromonaphthalene
ferrocene
(approximately
produced
(?-C5H5)Fe(CO)21
via the ferrabenzene
mmol) and
The mixture
of the iron complexes
ferrocenes
-PhCLi=CHCH=CLiPh
(33
sodium
have been investigated,
except propyne,
characterisation
has
glycol
powdered
tetrahydrate
mmol) were added.
of iron atoms with 2-butyne,
methylphenylacetylene
greater
of polyethylene
for one hour to give ferrocene
The reaction
process
amount
of ferrocene
in dimethylsulphoxide,
(67
1,3_cyclopentadiene stirred
for the preparation
complexes complexes.
This difference between and the correspondThe effects
of
ligands were also discussed
[85].
273
Ph
Fe
6.2
6.1
6.3
7. REACTIONS
OF FERROCENE
A study has been carried by olefinic produced
generated
ethylferrocene
in concentrated diazonium
[86].
hydrocarbons
ethyl radicals,
and diethylferrocene
salts prepared
with 2-methyl-5-
The reaction
[87].
Ferrocene
amines
and l,lfi-di-substituted
and -6-benzothiazolyl,
with
at 205-230°,
acid has been treated
from heterocyclic
Mono-
of ferrocene
of ferrocene
from diethylmercury
hydrochloric
cenylheterocycles.
out on the alkylation
with to give
ferro-
ferrocenes
2,3,3-trimethyl-5-indolenyl,
2-methyl-5- and -8-quinolyl groups were obtained [88]. A series 6 of (7 -arene)($-cyclopentadienyl)iron cations has been prepared from ferrocene Ligand
exchange
Rsferencesp.317
and subjected reactions
to a spectroscopic
between
ferrocene,and
study [Sg]. dibenzodioxin,
274
Q0
2+
Fe
Fe
h
Fe
0
7.1
phenoxathiin
h
or phenoxazine
-cyclopentadienyl)iron
produced
cations
X = NH, Y=S) respectively. complexes excess
was compared
of ferrocene
corresponding dications
reversible organic
carbon
intercalation detonation
and provided
process
[ql].
when mixed with
the
of ferrocene,
dioxide
fluoroborate
the basis of a Tetranitromethane
ferrocene
Thus tetranitromethane,
in solution
O.Olg, was mixed
contained
and nitrous
nitrogen,
oxygen,
oxide [92].
carbon
The hydro-
have been displaced
to form pentakis(trifluorophosphine)iron
tetrafluoroborate
from ferrocene
and HBF4.0Et2
in
0.2m1, when an explosion
SALTS AND MIXED-VALENCE
Ferrocenium yield
reaction
have been used as oxidizing
in bis(pentadienyl)iron
trifluorophosphine 8. FERROCENIUM
When a large
exchange
Thus stage 5 graphite
The gases evolved nitrogen
ligands
route.
of these
[90].
compounds
ferrocene
solvents.
occurred.
x=s, Y=O;
of preparation
with an alternative
ferrocene.
with a 2oo/osolution dioxide,
X=Y=o;
This method
(7.2) were obtained
oxidized
underwent
the (q6-heterocycl_e)(15-
(7.1;
(q6, 76-heterocycle)bis($-cyclopentadienyl)
towards
smoothly
7.2
was used in the ligand
Graphite-acceptor agents
0
SALTS
has been prepared in nitromethane
in 93%
[94].
by
[93].
275
8.1
The heterogeneous in saturated
oxidation
hydrocarbon
of ferrocene
solutions
solution
of ferrocene
and bismuth(II1)
oxidized
by molecular
oxygen
ferrocenium -black
by X-ray
precipitate.
-valenceT(-bond -ferrocene
spectra bridged
compounds.
Q Fe
8.2
in acetone
of sunlight
which
A was to the
formed a blue-
The salt was characterized
have been recorded and 6-bond
Intervalence
bridged
for nineteen
mixed-
di-, tri- and tetra-
electron
0
Fe
(IV) oxide
[95].
[96].
crystallography
The near-IR
bromide
in the presence
salt [(7-CsH5)zFe]q[Bi4Br16]
crystalline
on manganese
has been studied
Fe
8.3
transfer
was evident
276
in all of the Z-bond species.
derivatives transition through
was attributed
space mechanism.
Among
transfer
azoferrocene,
transition (8.2;
compounds
(Sol),
CH=NN=CH, spectroscopy. 8.3;
n = 1;
were characterized [‘8].
[97].
ferrocenes
by cyclic voltammetry,
and Moessbauer
includi.ng (8.2;
at room temperature
the
and diferrocenylketone CPh=CPh,
the
to a
exhibiting
= 13, tetracyanoquinodimethane,
-5,&dicyanobenzoquinone)
while
1,2-diferrocenylethene
CMe=CMe,
spectroscopy,
n = 1, X
mechanism
n = 1, 2) and the bridged
of the complexes
bridged
bridged
was attributed
the compounds
were,
n = 1, 2) have been studied
IR and electronic
CPh=CPh,
compounds
l,l-diferrocenylethene
Y = Hg, PPh, CH=CH,
CMe=NN=CMe,
in the?t-bond
to a through-bond
bridged
The biferrocenes
Several
and some of the f-bond
transition
in the c-bond
electron
(8.3;
bridged
The near-IR
Y=
2,3-dichloro-
as mixed-valence
Cyclic voltammetry
and
8.4
visible
and near-infrared
electron
transfer
complexes
(8.4;
series 2+/+/O/-
inthe
spectroscopy
ferrocene-tricobalt
R = Me, Ph). with specific
electrode
species were stable.
electrolysis
were used to obtain
found that both the ferrocenyl cations
[l+,O]
observed
intervalence
had localized were
however
oxidation
the cationic
moiety
transitions
formed a redox
potentials,
Chemical
species,
only
and it was
and the Co3C cluster
as redox sites in the dications
-valence
carbon cluster
Both complexes
the cationic
behaved
have been used to examine
[l+,l+]. valence
The mixed-
sites and the
consistent
with the Hush
277
model
for a class II species
electron
transfer
Decomposition Fe-C2(CN)4
optical
where
(v-C5H5)25 . phase of the
to be a ternary
D and A are donor and acceptor
type [D+][Do_5A-3, respectively. The crystal found to be composed
complex
gave the salt [(q-C5H5)2Fe]r
which was considered
(i) ferrocenium
unsymmetrical
of the charge-transfer
in ethyl acetate
[(NC),C=CCNO]'
displaying
C-91.
structure
was determined
c;' one-dimensional
segregated
ions and (ii) alternating
(tricyanoethenolate)2:ferrocene
stacks
1:2:1
molecules
and it was
stacks
of;
ferrocene:
[loo].
The &-
Ph
Ph
and
8.5
(8.5 and 8.6)
trans-isomers reactions
at almost
underwent
the same potentials
and these were attributed indicative
that the intervalent interaction possible
The
transfer.
It was concluded from a Co(I)-Fe(II1)
arose
in the 2+ ions because
Fe-Fe interaction
was not
[loll.
9. FERROCENYL Several
CARBENIUM
(9.1;
Referenceap.317
IONS
diferrocenylcarbenium
Ph, X = BF4,C104) the salt
couples.
gave rise to a band in the near
of intervalent transfer
redox
in the range 0.30-0.55V
to the Fe(II)-Fe(II1)
l+ and 2+ ions of both isomers infrared
two successive
salts
have been prepared
(9.2;
by heating
R = H, Me, Et, Ph, X = BF
4'
R = H, Me, Et, ferrocene
with
C104) in acetic
acid.
+ I 1
278
_
Fe
CR+
X-
Fe
2
9.2
9.1
The salts ponding double metal
(9.2) underwent
9.3
alkaline
diferrocenylmethanols resonance
technique
participation
ferrocenyl
in the stabilization
participation.
chemical
a sensitive
Factors
shift differences
rehybridization
were
caused by the electron in the cyclopentadienyl
were the cations
hydrolysis aqueous
(9.3;
ci-deuterium kinetic
significant
cyanide.
bonding
ligand.
n = 3;
chloride
in water
containing
ion [104].
other metals
metal
complexes
(metalloids) [lO.l;
n = 21 has been prepared
Mn(II),
of acetoacetylferrocene
with Fe(N03j3,
by the
Cu(OCOCH3),
Ferrocenyl-@-diketonate
respectively
ligands
R = Me, CF3) have been used to prepare
zirconium titanium
and hafnium complexes
[105].
M = Fe(II),
and Mn(OCOCH3)2 (10.2;
and
that there was no
the iron atom and the c(-carbon atom
of transition
M = Cu(II),
reaction
A large
effect has been found on
CHEMISTRY
(i) Derivatives A series
effect of the Among the species
R = H, Me, Ph) [103]. isotope
in the ferrocenylmethylquinolinium 10. FERROCENE
the large
effect caused by
withdrawing
It was concluded
between
a
cJ-orbitals and
of ferrocenylmethylquinolinium
methyl
direct
for the evaluation
the shielding
of the iron non-bonding
substituent studied
tool
spanned
active in producing
deshielding
secondary
NMR
of 57 Fe-enriched
The 57 Fe resonances
carbocations.
to the corres-
The 13C{57Fej
has been used to investigate
1200 ppm range and provided ofiron
hydrolysis
[~oz].
complexes.
(10.3;
titanium,
The bis(7-cyclopentadienyl)-
R = Cl, CH2NMe2)
were also prepared.
279
-0c I
0
‘0 --, -
COCH2COR
0'
Fe
M
6
Fe
COCH2COR
0
n .
10.1
10.2
The complexes were characterized by mass spectrometry [106]. 7 Reaction of the ferrocenyl-hydrazones (10.4; RL = H, Me; R2 = Ph, ~-cl-, E-NO~-, E-HO-C~H~, 4-pyridyl) with copper(U) acetate produced the corresponding copper(I1) complexes (10.5) c1071.
Reaction of the ferrocenylhydrazones (10.6;
_4A-p 6
:'@J
R = Ph,
~I'NNHCOR~
6
-L 10.3
10.4
4-ClC6H4, 2-02NC6H4, 2-HOC6H4, pyridyl) with tin(I1) chloride or R2Sn0, where R = Bu, octyl, produced the corresponding coordination complexes (10.7; R1 = Ph, 4-ClC6H4, 2-02NC6H4, 2-HOC6H4 , pyridyl; R2 = Cl, Bu, octyl) [108]. The same ferrocenyl-hydrazones (10.6) also formed stable complexes with triphenyltin acetate. The structure of the complex depended
RefeIe.ncesp.817
280
CH=NNHCOR
Fe I Fe
0 0
10.6
on the substituent tin(W)
complexes
species
[109].
Terminal conditions
R.
Both octahedral
and trigonalbipyramidal
were
formed together
with acetoxy
olefins
have been hydrogenated
bridged
under mild
by using dichloro(triphenylphosphine)[l-(N,N-o(-dimethyl-
aminoethyl)-2-diphenylphosphinoferrocene]ruthenium(II) catalyst
[llO].
Several
substituted
Fe
ferrocenylnitriles
as a have been
281
prepared and used as ligands to form (NH3)5Ru(II)nitrile complexes in which intervalence transfer was investigated by electronic A weakly coupled Class II description absorption spectroscopy. was used to account for the observed behaviour [ill]. The
10.8
10.9
hydroformylation of ally1 alcohol has been carried out using several rhodium-phosphine catalysts. l,l'-Bis(diphenylphosphinyl)ferrocene was found to be one of the efficient phosphines in the catalyst [112]. The hydroformylation of 1-hexene in the presence of HRhCO(PPh3)3-bidentate phosphine ligand catalysts has been investigated. A good linear Hammett free-energy relationship was obtained for 1,l '-bis(diarylphosphino)ferrocenes with electron withdrawing substituents. These catalysts gave higher rates and selectivities to linear aldehyde formation [llf. The (z)- and (-)- ferrocene-palladium complex (10.8) has been treated with the sodium salts of several amino acids, RNHCHMeC02Na, to form the amino acid and dipeptide complexes R = H, NH2CH2C0, NH2CHMeCO) [114]. The optically (10.9; active ferrocene analogue of prostanoic acid (10.12) has been prepared from the ferrocene-palladium complex (10.10) by way of the intermediate keto-ester (10.11) [115]. Organozinc reagents, prepared from the reaction of secondary alkyl Grignard reagents (ArRCHMgCl, where Ar = Ph, E-MeC6H4; R = Me, Et) and excess zinc halides were treated with vinylbromide in the presence of the chiral ferrocenylphosphine-palladium complex (10.13) as The asymmetric cross coupling products (10.14; a catalyst.
282
NMe2 I
IEt3SiH
Fe
10.12
R1 = H, Me, R2 = Me, Et) were obtained excess
[ 1161.
The enantiomeric
formed complexes L-aspartic diglycine produced
glycinate
complex
[117].
with the acid chlorides Treatment
produced
The benzoylation
combined
palladium
of ferrocenylcopper Acylation
64
derivative
ethylenediamine
complex
(10.8) L-lysine,
XC H COCl, where X = E-B', E-MeO, the corresponding
Slow crystallization produced
The glycine
and some biferrocenyl.
of ferrocenylcopper
diferrocenyl
complex glycine,
to form a hexacoordinated
benzoylferrocene
g-NO2, z-No2,
dipalladium
with amino acids including
acid and L-cysteine.
with sodium
in up to 86% enantiomeric
ferrocenylketones
with adipoyl
chloride
(10.15).
gave the
(10.16) [11_8]. of the dilithioferrocene-tetramethyl-
(T?'IEDA)adduct
(10.17)
from ether solution
[(7-C5H4Li)Fe(7-C5HjLiCH(Me)NMe2)]~[LiOEt]2[TMEDA]2.
283
Me
Fe
10.13
10.14
The structure of this latter complex was determined by X-ray The structure consisted of discrete molecules analysis. possessing exact C2 symmetry; each containing four ferrocene moieties, ten lithium atoms, two TMEDA units and two ethoxy groups. Each of the five independent lithium atoms achieved a distorted tetrahedral coordination in a different way. An extremely short Li-C bond (2.048) was observed [119].
qco
ax
~co’cH2’4c~
Fe
10.15
10.16
Treatment of thel,l'-dilithioferrocene (lo.181 with mercury(I1) chloride produced the ferrocenophane (10.19) [1201. Lithiation of 1,2,3,4,5-pentamethylferrocene (10.20) followed by condensation with tetrachlorosilane produced the ferrocenophane (10.21).
R8fsrsacap.917
284
10.17
This
10.18
ferrocenophane
was used to derivatize
platinum
and n-type
silicon
platinum
electrodes
exhibited
waves
consistent
electrodes
2 (cyt Cox)
The functionalized oxidation reduction
the one-electron n-type
redox couple.
reauction
photoanodes
of cyt sred upon illumination in the dark.
cyclic voltammetry
to ferrocytochrome
silicon
C (cyt Cred) effected
electrodes
2
10.20
These
of horse heart
and effected
The derivatized
CH2NMe 10.19
of
The functionalized
persistent
with a surface-confined
effected
ferricytochrome
electrodes.
the surface
the uphill
cyt sax were durable
285
Fe
Sic12 10.21
10.22
and lost little activity with repeated use [121]. Metalation of azaferrocene with n-butyllithium gave a mixture of 2- and l'-lithio- and the 2,1'-dilithio-intermediates which were characterized by treatment with methyliodide 'cogive the corresponding methyl- and dimethylazaferrocenes. The predominant product was the 2-methyl compound (10.22) [122]. The phosphonoferrocene (10.23; Y = OH) has been treated with triphenylphosphine in HBF or in HClO and CH Cl to form 2 2 4 4_ the phosphonium salts (10.23; Y = PPh;BF4 , C104-) respectively
Q-
9
FHP(OEt)2 Y
0
F;e
t,
Q0
9 ?ph3
CP(OEt)2
Fe
c!l
0
0
10.23
References p. 317
10.24
286
Fe
1
.
Fe
PX
6 0
6
which were converted
by sodium
secondary
phosphine
hydride.
Several
(10.25; related
X = Cl) was reduced
(10-25;
iodide
was converted
the alkali
spectra alkali of
cations
complexes indicated
ferrocenylmethylchloride
produced
the diquaternary
hydride
M = Na, K).
solvents group.
These
and the NMR between
the
The reaction
with bis(diphenylphosphino)methane
salt
(10.30).
salt with strong bases was investigated Mono- and di-phosphaferrocenes, compound
(10.28)~
an interaction
and the ferrocenyl
with
the phosphonium
or potassium
(10.29;
in some organic
of the solutions metal
were reported
produced
produced
metal
to the
aluminium
into the ylide
of this ylide with sodium amide were soluble
(10.26)
by Moessbauer
X = H) with lithium
Reaction complexes
x = Cl)
of bis(diphenylphosphino)methane
[ 124, 1251. ferrocenyltri.methylammonium (10.27) which
(10.24)
(10.25;
to form the salt
compound
transformations
The reaction
salt
to the ylide
chloride
chloride
as a ferrocenyl
The chloride
2
carbonate
[ 1231. has been treated with aluminium
spectroscopy.
4
10.26
The ferrocenylphosghorus(II1)
which was confirmed
AlCl -
0
2
10.25,
P"
(10.31) have been studied
The reaction
of this
[126].
including
the tetraphenyl
by 'H and 31P NMR and
Introduction of a phosphorus atom into Moessbauer spectroscopy. the cyclopentadienyl ring caused a reduction in quadrupole splitting
by comparison
(10.31) underwent high quadrupole
with
ferrocene.
phenyl ring protonation
splitting
terms of iron participation
The diphosphaferrocene in CF3S03H
and the
for this species was interpreted in the stabilization
of the
in
+
287
cH2P(Ph)2=CHPPh2
H,P(Ph),CH,PPh2 IFe
Fe
10.28
10.27
2c1-
10.29 6-complex
[127].
10.30
The preparation
5-cyclohexadiene)metal
complexes
of the l,+dibora-2,(FcBC~H~BFC)M(CO)~,
Fe
10.32
Refexencssp.317
where
288
M = Cr, MO, W, and (FcBC6H4BFc)M(CO)3, has been described. benzene
moiety
v6-bonded
(ii) General
In all these complexes
(10.32) behaved
ligand
where M = Fe, Ru, OS,
as a strongly
the 1,4-diboraback-donating
[128]. Chemistry
The ferrocenylmethylthio-carboxylic Rl = H, R2 = CH,2C02H, C6H4.C02H-2)
acids
(10.33;
have been converted
to
CHR1SR2
10.33
formylferrocene
by oxidation
of the carboxylic
acids
Rl = Me, R2 = CH2C02H)
with manganese
(10.33;
dioxide.
Reduction
RI. = H, R2 = CgH4.C02H-2;
gave methyl-
and ethyl-ferrocene
respectively [129]. The base catalysed condensation of formylferrocene with g-(CH3CO) C H produced the cyclic ketone 264 was obtained. (10.34), in th e presence of acid the olefin (10.35) Similaracid and base catalysed condensations were carried out with g-CH3COC6H4C6H4COCH3-g and 1,8_diacetylnaphthalene [130]. Treatment of acetylferrocene with POC13 and Me2NCH0 gave a
10.36
10.37
mixture of the chlorovinylferrocenes (10.36; R = H, CHO) which gave ferrocenylacetylene with sodium hydroxide. Ferrocenylacetylene was coupled in the presence of copper(I1) to form the diacetylene (10.37) [131-j. Decomposition of the dicarbonyl compound (10.38) with 1:l MgBr2-Mg(OMe)2 or MeOMgBr produced
HOMe F Ph Fe
10.38
Referencen p. 317
10 -39
10.40
220 the ether (10.39) as the major product. In a similar decomposition with C5H10NMgBr the amine (10.40) was obtained [l32]. Ferrocene polyethers (10.41; n = O-3) have been prepared by treatment of l,l'-diacetoxyferrocene with the halid,es Me(OCH2CH2)nX, where X = halogen. Ths polyether (10.41; n = 3) was effective in the extraction of unipositive cations. The order of efficiency was: Ag+> Tlf> Cs+> K+> Li+> Na+ The diferrocenyl polyethers (10.42; n = 2-4) were obtained by treatment of the potassium salt of hydroxyferrocene with the dibromides Br(CH2CH20)nCH2CH2Br in DMF. These polyethers (10.42) were not useful as extractants for metal cations [133].
Q-
0(CH2CH20),CH2CH20
0
Fe
Fe
Fe
10.41
10.42
p-Dicarbonyl derivatives of ferrocene have been used to prepare the ferrocenylheterocycles (10.43; 10.44 and 10.45; Ferrocenylmethyl compounds (10.46; R = H, Me, Ph) [134]. R = Me, Ph, ferrocenyl) have been oxidised to the corresponding ketones (10.47; R = Me, Ph, ferrocenyl) with bis(triphenylFerrocenylethenes were silyl)chromate(VI), (Ph3Si0)2Cr02. oxidatively cleaved by the same reagent to aldehydes [135]. Oxidation of the alcohols (10.48; R = H, Me, Ph, substituted Ph, OMe, CMe3) to the corresponding ketones (10.47; R = H, Me, Ph, substituted Ph, OMe, CMe3) has been investigated using [Bu~N]~[C~~O~], [PhNH3][Cr03C11 and [Bu4N][Mn04] as the Acylferrocenes have been treated with thioreagents [136]. glycollic acid and the ethyl ester to form the dithio compounds l,l'-Diacylferrocenes (10.49; Rl = H, Me, Ph; R2 = H, Et).
291
Fe
10.44
10.43
10.46
10.45
Reduction of the compounds (10.49) underwent the same reaction. with lithium aluminium hydride gave the corresponding diols
Q-
COR
0
Fe
10.47
Raf-p.817
Q-
CHROH
0
Fe
10.48
292
Q-
R1(SCH,C02R2),
CR(ASCH~CH~OH)~
0
10.50
10.49
(10.50;
R = H, Me, Ph) [137]. catalytic hydrogenation
The
diethylferrocene Ti,Fe-Ti, active
Cr-Ti,
catalysts
on nickel-aluminium-metal Cu) has been investigated. was obtained
of diacetylferrocene
1,2-disubstitvted
[139].
ferrocenes,
R1 = Me, R2 = (cH~)~oH] [10.51;
pressure
Enantiomeric
(metal =
One of the most
catalyst
of hydrogen
Hydrogenation in propan-2-01 gave 85-98s
and diastereomeric
for example
have been prepared
R1 = CO(CH2)5C02Et,
t0
catalysts
when M = Ti [138].
on a nickel-rhenium
at 78'C under one atmosphere diethylferrocene
of diacetylferrocene
the alcohol
R2 = H] via reduction,
amination,
. >5C02Et
Fe
R2
I 2
10.51
10.52
rlO.51;
from the ester
293
~cH2cH20H
p
Fe
Fe
Fe
cyclopalladation
with sodium
(10.52)
amination
[140].
ferrocene
with phosphorus(II1)
produced
of this cyanide
followed
tetrachloropalladate(I1)
the dimer
cyanide
by carbonylation
The reaction
chloride
of the diacid
by potassium Hydrolysis
obtained [141].
such as the secondary
R = Me, Ph) have been converted
gave the
The cyanide was also used
l,l'-bis(@-aminoethyl)ferrocene
Ferrocenemethanols amines
followed
l,l'-bis(cyanomethyl)ferrocene. and reduction
to give
and reductive
of l,l'-bis(hydroxymethyl)-
(10.53) in 56% total yield.
to prepare
10.55
10.54
10.53
diol
ph:
CHROH
to the corresponding
(10.55; R1 =. Me, Ph, R2 = Me;
(10.54;
alcohols
tertiary
Rl = Ph, R2 = Et) by
_
Q-
1
CHMe
0
Fe
. 10.56
Referencea p.
317
10.57
NH
n
10.58
3-n
Fe
lG.61
10.60
10.59
treatment with hydrogen bromide and then dimethylamine or diethylamine [1423. Treatment of l-ferrocenylethanol (10.56) with dimethylamine and dicyclohexylamine in the presence of hydrogen bromide gave the tertiary ferrocenylethylamines (10.57; When the reagent was ammonia a mixture of the R = Me, C6Hll). primary, secondary and tertiary amines (10.58; n = 1, 2, 3) was Use of the optically active amine d-(+)-PhMeCHNH2 obtained. led to the formation of diastereoisomeric ferrocenylethylamine Dehydration of the alcohol (10.59) with products [143]. SnC12-HCl gave 96% of the trans-isomer of the olefin (10.60). When a mixture of the cis- and trans-isomers was treated with
Q0
FHcHzoH OH
Fe
0
6
10.62
10.63
Q-
NHCOCH3
NCOCH3
NH
0
1. NaNH2 Fe
Fe
2. FcBr, CuBr pyridine
KOH EtOH
>
10.64 10.67
10.66 / KOH
1. NaNH2
H2°
2. FcBr, CuBr pyridine /
Q-
NH2
0
Fe
6 0
10.65
3 10.68
SnC12-HCl, 94-5% of the trans-isomer was produced (10.60). Reaction of the cis- and trans-isomers with H202-KOH produced the cis- and thexans-acrylamide (10.61) [144]. Oxidation of vinylferrocene with tetrabutylammonium permanganate in dichloromethane produced the diol (10.62) [145]. The hydrazides (10.63; R1 = H, R2 = Et, Br, Ph; Rl = Me, R2 = Ph) have been prepared from ferrocenoyl chloride and z-RlC6H4NHNHCOCR;OH [1461. The reaction of bromoferrocene with the sodium salt of an amine or amide in the presence of copper(I) bromide/pyridine has been used as a general method for the preparation of Ferrocenylamine (10.65) was prepared by the ferrocenylamines.
296
Fe
6
0
"MN
2 lo.69
hydrolysis
10.70
of N-ferrocenylacetamide
(10.67) and tertiary
(10.68)
from the same starting diferrocenylamide
(10.64).
ferrocenylamines
material
the intermediate
The reaction
of chloromethyl-
(10.66) [147].
the corresponding
and 10.70)
photooxidation
with 4,4'-bipyridine
ferrocenylmethyl
Inhibition
[148].
by aliphatic
of ferrocenyl-substituted
been reinvestigated.
The aliphatic for OH radicals
the oxidation
[149].
11. BIFERROCENES,
FERROCENOPHANES
The electronic iene
structures
The results
semiempirical ization
were
which
derived
(11.1) has been estimated. ferrocenes theoretical crystal
to be classified models used
and molecular by X-ray
FERROCENES
spec-
calculations
predicted
using
large reorganlocalized
MOs
The time of hole exchange from biferrocene
This has allowed
for mixed valence
structure
the binuclear
species
of a picrate cation
crystallography.
in
and the complex
in a way that corresponds
salt of the [O.O]ferrocenophanium determined
in
and biferroceny-
events of highly
with major iron 3d amplitudes. the l+ and 2+ cations
AND ANNELATED
by He(I) photoelectron
for ionization
has
has been shown
which were involved
compared with
INDO MO methods
effects
(10.69
of the
carboxylic. acids
of biferrocene
(11.1) have been examined
troscopy.
derivatives alcohols
alcohol
to act as a scavenger process
were obtained
(10.64) through
and l,l'-bis(chloromethyl)-ferrocene produced
The secondary
to the
[150].
The
hemihydroquinone
(11.2) has been The Fe-Fe distance
was
297
Q-9 Fe
Fe
Fe
Fe
11.2
11.1
34 pm shortei
than in the neutral
some Fe-Fe interaction the cyclopentadienyl
ferrocenophane
in addition
rings
to the interaction
[151].
Adducts
and 1,1,2-tetramethyl[2]ferrocenophane were
prepared
by treating
X = Cl, I, CN. was strong atoms
direct
[152].
combined
with tin(IV)
[2]ferrocenophane Moessbauer of direct adducts
spectroscopy
interaction
Ferrocene, adducts
quadrupole
between
splitting
Fe-Sn bonding.
Intramolecular ferrocene
using
The red-orange
large 57Fe
which was interpreted
in terms
and [3]ferrocenophane
the ferrocenium
and
[153].
reductive
lowvalent
and [3]ferrocenophane
an unusually
The ferrocene
cations
that there
the iron and mercury
were dark green and contained
[3]ferrocenophanium
with HgX2 where
to form adducts.
showed
between
of [2]ferrocenophane
suggested
[Zjferrocenophane
chloride
indicated
with mercury(II) salts
the ferrocenophanes
Moessbauer
which
coupling
of l,l'-bis(o-formylphenyl)-
titanium reagents
gave E-
and
anti-[0~orthocyclo[2]orthocyclo[O](l,l1)ferrocenophan-7-ene~ These were
and related examined
interactions
ferrocenophanes
prepared
by NMR and UV spectroscopy between
the two benzene
of l,l'-bis(chlorocarbonyl)ferrocene the ferrocene proportions
cryptates
bis(aminophenyl)ethers (11.4;
n = 0, 1, 2).
Fl.eferenceap.317
[154].
combined
The yields
features
gave
and
by the reaction
with
to give the macrocyclic Structural
Treatment
with diaza-18-crown-6
were determined
The same reagent
reactions
for %-electronic
rings
(11.3 and 11.5).
of these products
temperature.
by similar
ethylene
glycol
ferrocenophanes
of the products
Q- T0 CON
0
0
Fe
0
0
CON
dJ
11.3
(11.3
and 11.4) and dynamic processes within the molecules were examined by 1H and 13C NMR spectroscopy [155, 1561. The diacetate (11.6; R = COMe) has been treated with the dichloroethers, ClCH,(CH2OCH,),CH,Cl, where n = O-3, in the presence of potassium hydroxide to form the chloroethers (11.6; R = CH2(CH20CH2)nCH2C1. These were then attacked by sodium sulphide to give the polyoxathiaferrocenophanes (11.7; n = O-3) and the binuclear polyoxadithiaferrocenophanes (11.8; n = O-3). The ferrocenophane (11.7; n = 3) was effective in extracting unipositive cations with the following order of efficiency: Tl+ >) Rb+, K+> Cs+> Na+)Li+ [1571* The polyoxaferrocenophanes (11.9; n = 0, 1, 2, 3, 4) were prepared in one-step by reaction of l,l'-diacetoxyferrocene with the appropriate ether ClCH2(CH20CH2),CH2Cl. The ferrocenophane n = 4) formed crystallAne 1:l complexes with lithium, (11.9; sodium and potassium thiocyanates. Spectroscopic data indicated that in these complexes there was possibly some interaction between the iron atom and the complexed alkali metal cation [158]. The polyoxa-ferrocenophanes (11.10 and 11.11; n = 2, 3, 4) and (11.12; n = 1, 2) have been prepared from l,l'-bis(hydroxyThe complexing ability of these compounds methyl)ferrocene. with alkali and transition metal cations was investigated [1591. The cyclization of 1-acetyl-l'-(&-chlorocinnamoyl)ferrocene to the ferrocenophane (11.13) was catalysed by a variety of acid The base catalyzed condensation of 1,3catalysts [160].
299
Q-
f‘ on0 /\I
CON
0
NOC
L”jJoJ
Fe
(‘ ono /\1
CON
L
-2 0
Fe
NOC
dl 0
11.5
ToI?
p&y
lt$LOR &oqAn
11.7
11.6
-ferrocenediacarbaldehyde with l,+diacetylferrocene using the high dilution technique produced the ferrocenophane (11.14).
11.8
Referencap.817
11.9
11.12
11.11
This compound hydrogenated
was reduced
with the 3-arylThe reaction
was completely
to substituents
at C(3).
giving
alkyd groups were
The chair conformation, bonding
in which
predominated
(11.17) [ 1621
have been prepared
cis
with strong
in the hydroxy-
A series
the two I-cyciopentadienyl
rings,
the corres-
R2 = Me, Et, n-Pr, i-Pr,
the introduced
hydrogen
derivatives
by biphenyl
reagents
Et) has been investigated.
(11.16) and this was the o;*ly conformer
dihydroxy phanes,
Me2CHCH2,
stereospecific
(llJ6 and 11.17;
t-Bu) where
intramolecular
[161].
of Grignard
and 3-alkyl-[5]ferrocenophane-1,5-diones
alcohols
CH2=CHCH2,
ketones
of the reaction
R1 = Ph, E-MeOC6Hq,
(11.15;
and then catalytically
to give [303](1,3)-ferrocenophane
The stereochemistry
ponding
with LiA1H4-AlC13
present
in the
of ferroceno-
rings were linked
via intramolecular
coupling
301
Cl
of the corresponding For example
reductive
Rl = CHO, R2 = H; derivatives
foray1 compounds
(11.19 and 11.20) respectively.
transannular
11.15
References
compounds
ferrocenophanes
have been prepared aldehydes.
p.
317
of the dialdehydes
R1 = 3, R2 = CHO) produced
of these and related Several
coupling
with a TiCl 4-Zn r'eagent.
including
by reductive
UV-visible electronic
were
examined
The structures by spectroscopy
the acetylenes
coupling
spectroscopy interactions
11.16
(11.18;
the biphenyl [ 1631.
(11.21 and 11.22)
of the corresponding
was used to investigate
11641.
11.17
11.18
11.19
11.20
11.21
The pentabridged ferrocenophanes (11.23 and 11.24) have been prepared from the propionic acid (11.25). The structures of the ferrocenophanes (11.23 and 11.24) were confirmed by X-ray analysis. The crystal and molecular structures of both compounds were almost identical and both contained a rotational disorder about the axis of five fold symmetry through the two Formylferrocene has been I-cyclopentadienyl rings [165]. condensed with the appropriate formylparacyclophane to give the cyclophane complex (11.26) and the diparacyclophane complex (11.27) has been obtained by complexation of the appropriate The reaction of tetrakis(triphenylligand with iron [1661. phosphine)palladium(O) with 1,2,+trithia[3]ferrocenophane The structure produced the heterobinuclear species (11.28). The ferrocene of this complex was determined by X-ray analysis.
303
11.23
11.22
CH2CH2C02H I
11.24
11.25
moiety was slightly bent and the geometry about the palladium atom was a distorted square plane [167]. Trithiaferrocenophane (11.29) has been treated with dodecacarbonyltriiron to form the dithiolatodiiron complex (11.30) [168]. l,l'-Ferrocenedithiol has been used to prepare the polythiaferrocenophanes [11.31, X = (CH2)2, (CH2)2 S(CH2)2, (CH~~~S(CH~~~~(CH~~~, n = 2,3; (cH2)3s(CH2)ns(CH2)3, The spectroscopic properties of these compounds n = 2, 33. The [5]ferrocenophane (11.32) has been were discussed [169]. obtained by treatment of ferrocene-l,l'-dithiol with pentaBridge reversal in the complex (11.32) erythritol tetrabromide. Diastereomeric has been examined by 1H NMR spectroscopy [170]. oxathiaferrocenophanes, for example the complex (11.33), have
11.26
11.27
Q-\
S
S
0
Fe
@d-
\
PPh3
o0
11.28
S
S
/
11.29
11.31
305
11.32
11.33
been prepared by reaction of 1,l '-bis(hydroxymethyl)ferrocene with dithiols containing ether linkages [171]. 1,2-Bis(hydroxy-
CH20H
Q 0
Fe
Referencerp.317
306
11.40
11.39
11.38
methyl)ferrocene (11.34) has been attacked by hydrogen sulphide to form the dithiaferrocenophanes (11.35 and 11.36) [172], The cleavage of the [l]-ferrocenophane (11.37) &th phenyllithium produced 1-lithio-1 I-diphenylphosphinoferrocene which was coupled with acetyl chloride to produce the heteroReduction of this annularly substituted acetylferrocene (11.38). ketone produced the corresponding alcohol and attempts were made to convert this to the amine (11.39), but the yields were An alternative synthetic route to the amine (11.39) small. The ferrocenophane (11.40) was treated with was devised.
Li
R1
Fe
11.41
11.42
307
phenyllithium at low temperatures and on hydrolysis the amine (11.39) was produced in good yield [173]. Treatment of the l,li-dilithioferrocenes r11.41; R1 = H, CHMeNMe2, CH(CHMe2)NMe2] with RzMC12(PhPC12, PhAsI2, Me3CPC12) produced the corresponding The crystal structures of these [llferrocenophanes (11.42). The mean tilt of the 7-C5H5 rings compounds were determined. in the phosphorus bridged compounds was 27.0' and for thezsenic derivatives 22.9' [174]. 12. FERROCHNE-CONTAINING POLYMERS Radical polymerization of l,l'-divinylferrocene (12.1) gave a homopolymer which was shown by 13C NMR and Moessbauer spectroscopy to be a cyclopolymer containing a three-carbon bridged ferrocene unit. When cationic polymerization was used then the polymer had an acyclic structure [175]. Divinylbenzene and vinylferrocene have been copolymerized at 680'~ and 125 MPa and the resulting copolymer was subjected to pressure pyrolysis to give carbon containing finely dispersed iron. The pyrolysis conditi.onsused determined the morphology of the carbons which consisted of fibrils, spheresand polyhedra [176]. The rate of intramolecular electron exchange between pendant ferrocenyl groups in poly(vinylferrocene) has been determined by an NMR The rate constant was determined line broadening technique.
9” 0
Pe
Refemllceep.917
Fe
308
Electroactive
as 6.4 x 10*[177]. ferrocene
(PPVF) films have been deposited
electrodes
for use in electrochemical
scopic and ellipsometric PPVF film surface demonstrated
were
studies.
independent
in the
oxidized
to
charge-potential
to the square
of the solvent in the presence
trifluoride molecular
etherate
weight
the polymer
Adducts electron
measurements
of ferrocene
underwent
cationic
of trifluoroacetic
of 8100-14700.
ethylene
material
the monomers
R1R2C=CH2
R2 = m-carbonyl,
and
conductivities (H,C=CRl),Z
1 R-
12.3
in and
was also present with
and tetracyanosusceptibilities
oxidation
of iron(I1)
and to
of the adducts were and polymerization
of
(R1 = ferrocenyl,
Z = 1,7-m-carboranediyl)
PPh
unsaturation
2,2'-(2,5-cyclo-
The magnetic partial
The preparation
high [180].
average
poly(l,l'-ferrocenylene)
such as iodine,
indicated
The electrical
iron(II1). relatively
acid or boron
Some residual
Fe(II)-Fe(III),
have been prepared. spectra
homopoly-
by 'H and l3 C NMR spectroscopy
of crystalline acceptors
and were
used [178].
hexadiene-1,4-diylidene)bispropanedinitrile Moessbauer
and ferrocenium
of their concentrations
to give a polymer with a number
was identified
some mixed valence,
spectro-
residues
l,ll-Diisopropenylferrocene merization
carbon
photoelectron
Ferrocene
that the activities
were proportional
on glassy
X-ray
vinyl-
foundto be appreciably
Equilibrium
ferrocenium.
c1791. various
plasma polymerized
have been investigated.
309
Treatment
of acetylferrocene
dehydration,
produced
of this monomer Products
oligomeric
products
between
underwent
in the presence
DTA at temperatures
(12.2).
were
were
and
evaluated
from the polymeric
in which
similar
catalysts.
Catalysts
The photochemical
complexes
Rl = H, R2 = OH)
A mechanism
characteristics
of this
[ 1841.
determined
and Photosensitizers
system
investigated.
dark reactions
in polymer
was proposed
ferrocene
of offset
composition [ 1861.
sensitivity
printing
has been prepared
or tri-t-butylferrocene
with
A similar
carbon
ferrocenes
[ 1871.
ferrocene,
dibenzylaniline
gave different wavelengths
good contrast or a mixture
[ 1881.
and relatively
They contained
a mixture
of mono-,
has
A light
from triethylferrocene and a toning
with high light
composition on exposure
Light sensitive
on polymethyl-
containing in a polystyrene to light of compositions
with
low cost have been developed.
of mono-,
di- and tri-t-butylferrocene
di-, tri- and tetra-isopropylferrocene
with tetrabromomethane
Fkferencesp.317
[l85].
plates
and tetrabromomethane
photoproducts
system
region was based
A light sensitive
system were
film which was suitable
tetrabromide
composition
in the long wavelength
have been
and the sensitometric
The ferrocene-tetrabromomethane
for the preparation sensitive
of the
layers
based photoimaging
been used as the basis of a photoimaging
together
and selectivity
Cobalt
(12.3;
and subsequent
ferrocene-tetrabromomethane
different
The
for the hydroformylation
reactivity
phosphines
the phosphine
OF FERROCENE
(i) Ferrocene
binder
R1 = H,
weight
13. APPLICATIONS
compound
(12.3;
and
The
8,900-161,000 amu showed catalytic that was molecular weight dependent [183-J.
with molecular activity
[182].
when appropriate.
as catalysts
to cobalt-triphenylphosphine formed
oligomers
and
The
by thermogravimetry
tridentate
they exhibited
of 1-hexene,
to Me2Si(CECH)2 catalyst.
in oxygen
to form complexes
chelating
were
and
R1 = Ph2P, R2 = Ph, n = 1, 2) combined with
octacarbonyldicobalt complexes
addition
characterized
l,ll-ferrocenylenephenylphosphine
ligands
by
ferrocenyllithium
of an H2PtC16
of up to 1000°C
R2 = Ph, n = l-4;
followed
The polymerization
[18l].
was also studied
from the reaction
methylphenylchlorosilane Ph2Si(CWH)2
with Li(SiPh2)4Li,
the monomer
and a toning
compound
[189].
310
In a related patent the composition contained methyl, ethyl or propyl acetylferrocenecarboxylate as the metallocene component. Low temperatures for development and short development times were claimed [190]. Ferrocenyldiphenylamine, diferrocenylphenylamine and triferrocenylamine (13.1; n = 1, 2, 3) respectively, have been dissolved in polystyrene or a polycarbonate and used to form electrophotographic layer materials with photoconductor properties [191]. Condensation polymers, such as poly(oxy-2,6-dimethyl-1,4-phenylene), have been solubilized by treatment with Cs salts, such as the Cs salt of ferrocene carboxylic acid.
\ & C02H
Fe
RPh3_n
Q-
PPh2
0
Fe
0
n
PPh2
Cl
13.2
CH~NM~~ 13.3
Irradiation at 435nm of the solubilized polymer films in the presence of dibromotetrachloroethane caused rapid darkening consistent with cation formation [192]. Asymmetric hydrogenation of the tetra-substituted olefinic acids R1R2C=CR3C02H (R1 = R2 = Me, R1R2 = CH2CH2, R3 = aryl) has been achieved with a catalyst system containing a coordination complex of rhodium, ruthenium or iridium and a chiral ferrocenyl-, ruthenocenyl-, osmocenyl- or For example, the olefin (13.2) pyrrolidinyl-phosphine ligand. was asymmetrically hydrogenated at 700 p.s.i. and 80'~ using a catalyst system containing [(7-norbornadiene)RhC1]2, the chiral ferrocenylphosphine (R,S)-(13.3), silver tetrafluoroborate and triethylamine [193]. A catalyst has been prepared, for use in the synthesis of ammonia, by the adsorption of potassium vapour and ferrocene The catalyst had much higher activity at on active carbon.
311
lower temperatures than a conventional iron catalyst. A linear correlation was observed between the ferrocene concentration and the activity increase. A Moessbauer study indicated the presence of ferromagnetic FejC and o&Fe with the at-Fe being the active centre [194]. 1-Benzoyl-1' -o-chlorobenzoylferrocene has been used as an intermediate in the preparation of l'-benzylferrocenecarbinol which was converted to the tricarbonylchromium complex and evaluated as a catalyst [195]. (ii) F errocene Stabilizers and Improvers Several ferrocene derivatives have been tested for their ability to prevent the ultraviolet induced aging of corrosion-protective films of low-pressure polyethylene on steel. The addition of acetyl-l,ll-diethylferrocene oxime to the polymer gave maximum resistance to ultraviolet aging and maximum protection of the steel from atmospheric corrosion [196]. A study has been carried out on the relaxation of stresses in modified polyethylenes. The mechanical properties of the polymer were improved by the addition of ferrocene [197]. Ferrocene has been used in the treatment of polyethylene and polypropylene wastes which were subsequently recovered [198]. The effect of ferrocene derivatives and cymantrene on the heat and radiation resistance of silicone rubbers has been investigated. o(-Methyl-@&dicyanovinylferrocene, l,l~-tetramethylsiloxanylferrocenophane and cymantrene increased.the heat and radiation resistance with the ferrocenophane being the most effective [lgg]. The incorporation of the ferrocenylamine thiocyanates (13.4; R = H, Me) into neoprene rubber produced vulcanizates with increased strength [200]. A small proportion of ferrocene or acetylferrocene and benzenesulphonic acid has been mixed with a formaldehyde-furfural-phenol copolymer and acetone to give a composition suitable for the treatment of wood. Samples modified in this way showed a loss in compressive strength and a low mass loss on accelerated aging [201]. Ferrocene or acetylferrocene, 0.5-1.5"/0, has been added to the same copolymer which was then used to retard the aging of wood [202]. A related patent described the modification of woudby the incorporation of the same copolymer containing a small proportion of benzenesulphonic acid and ferrocene to give a fracture-resistant
Reference8p.317
312
HRNHJ+ SCN-
Fe
6 0
13.4
material
[
2031.
derivatives
The addition
rate of emulsification A stabilizer
[204]. developed
[205].
-paraffin oil. readily
together
The results
by the alcohols
ferrocene
plasticizer
heated substrate
were discussed
the presence
(iii) Ferrocene Vanadium 2.12% vanadium
materials
in terms of the [206].
formed
Metallocene
copolymer,
with a
for electrophotography
atmosphere,
depositing
The gas carburization
[207].
vapour
speeded
the film on a
it in a reducing of steel products up the process
in
at a
[209]. in Analysis
has been determined by amperometric titration
with
in steels
titration
and iron were determined
potentiometric
in
thin films have been formed by evaporating
of ferrocene
lower temperature
and eight
additives
ions that were
and then heat treating
[208].
salt and
have been used to form the basis of
in an oxidizing
atmosphere
as antiwear
and the sulphides
transport
"$-Hematite magnetic ferrocene
with a combustible magnesium
such as styrene-vinylferrocene
charge-carrier
has been
of ferrocenyl-alcohols
have been tested
the
the mixture
emulsions
an oil soluble
of the ferrocenyl-carbenium
copolymers,
Vanadium
ferrocene
A series
ferrocenyl-sulphides
reduced
when air was blown through
benzyl alcohol,
a surfactant
oil mixtures
for fuel oil-water
that contained
emulsifier,
stability
of 0.05 wt.% of ferrocene
to 1:l water-lubricating
containing
with
ferrocene.
in nickel-based
ferrocene
O-14-
alloys
in 5-6M sulphuric
by acid.
313 Strong oxidizing agents such as chromium(V1) and manganese(VI1) interfered but large excesses of iron(III), molybdenum(V1) and relative to the vanadium(V) concentrations, did not copper( The concentrations of vanadium(IV) and interfere [210]. vanadium(V) present together in vanadium catalysts have been determined by a titrimetric method using a solution of ferrocene in propanol. Initially the vanadium(V) was determined amperometrically orpotentiometrically in a 5-6M sulphuric acid solution. After the addition of phosphoric acid the vanadium (IV) was determined by continuing the titration [211]. Iron(II1) and vanadium(IV) were determined in the presence of each other by amperometric or potentiometric titration with O.OlM ferrocene. Methods were developed for determining iron and vanadium in different alloys [212]. Ferrocenometric techniques have been used for the determination of standard reference materials [213]. Ferrocene has been proposed as a primary iron standard in volumetric analysis since it may be purified easily, it is resistant to oxidation and it is not hygroscopic [2l4]. Ferrocene has been determined by potentiometric titration with iron(II1) chloride in methanol containing perchloric acid [2l5]. Gold(II1) has been determined by potentiometric titration with a O.OlM ferrocene solution. Copper and a four fold excess of Ferrocene has been used as a silver did not interfere [216]. reducing agent for palladium(I1) and silver(I) in aqueous-organic solutions. A gravimetric procedure, using ferrocene, has been developed for the determination of these elements in palladium-silver alloys [217]. A ferrocene-modified platinum electrode has been used as a potentiometric sensor for &-ascorbic acid in an aqueous glycine buffer at pH 2.2. In recovery experiments with pure &-ascorbic acid the relative standard deviation was l.y/oand in the analysis of fresh orange juice the relative standard deviation was 6.1% A kinetic investigation of the oxidation of NADH by [218]; ferrocenium salts has provided an estimate of the Eat value (1.05 V vs. NHE) for the one-electron no proton couple NADH/NADHt [219]. (iv) Combustion Control The addition of metallocenes and related,compounds was
Referenceap.317
314
effective in reducing the smoke and hydrogen chloride evolved in the thermal degradation of poly(viny1 chloride). Nickelocene and dicyclopentadienyltitanium dichloride were more efficient in smoke suppression than ferrocene [220]. The combustion velocity of ammonium perchlorate based solid propellants for rocket igniters has been improved by using dibutylferrocene as a catalyst in place of Fe203 [221]. The use of diesel fuel containing 20-30 ppm of ferrocene was effective in replacing carbon deposits with catalytic iron oxide on the combustion surfaces of diesel engines. Subsequent operation with a lower concentration of ferrocene, 10-Q ppm maintained the iron oxide layer [222]. (v) Biochemical and Biological Applications The toxicity of the ferrocene hematinic (13.5) and its effects on the liver and adrenal cortex of the dog, rat and The hematinic (13.5) was monkey have been investigated. administered orally at dosages ranging from 0 to 500mg/kg/day to dogs, for two weeks, and to monkeys and rats, for six weeks. High-dose rats had distended abdomens due to enlarged livers while high-dose dogs and monkeys exhibited the following signs: emesis, depression, ataxia, anorexia and a high number of deaths [223]. The effect of the ferrocenyl group on the antimicrobial activity of (J-lactamic antibiotics has been investigated and the reaction conditions determined for the preparation of l,l'-ferrocenyldicarboxamidopenicillanic acid (13.6) and l,lf-ferrocenyldicarboxamidocephalosporanic acids (13.7; R = The ferrocene analogues of the CH20COMe, CH2S.CN2CS.Me) [224].
Q-i 0
Fe
S
13.5
315
C02H
b,
CONH
0
S
TT N
0
C02H
C02Na
13.7
13.6
antiinflammatory agents tolmetin, fenbufen, flurbiprofen and fenclofenac have been prepared and tested for biological The compounds exhibited little or no antiarthritic activity. or platelet antiaggregatory activity [225]. Analogues of enkephalin, substance P(SP) and bradykinin containing ferrocenylalanine, cymantrenylalanine and-tricarbonyl!7-cyclobutadiene)ironalanine have been prepared by solid-phase synthesis. The properties of these molecules were compared with those of the corresponding phenyl containing derivatives [226].
Q-
C02H
NPh
0
Fe
0
J5
13.8
Fe
316
Fe
13.10
Biologically
active
by treatment with
peptides
of the peptide,
ferrocenecarboxylic
followed
by cleavage
have been labelled
acid
(13.8) or cymantreneacetic
with HF-anisole
such as E-succinamidophenobarbital, ferrocenylmethylamine
have been combined with
and used to obtain antibodies
Ferrocenylmethanol eleven nitrogen
and +ferrocenylethanol
containing
and the ferrocenylimine
of HBF
to give a series
compounds
4
had bactericidal
Staphylococcus derivatives
and Candida
containing
species
Sphaerotheca
pyrethroids
(13.10;
@H2.C6H4SCBMe)
The products
fullginea
X = CH2CH2,
(+)-trans-chrysanthemic
activity
[229].
These
against
A number
of ferrocene substituents
For example,
benzoylferrocene
on cucumbers
[230].
CH2CH=CH,
have been obtained
propanecarboxylic
(13.9) in the presence
aryl, acyl and carboxyl
have been tested as fungicides. controlled
triphenylphosphine,
of onium compounds.
and fungicidal
alkyl,
have been treated
heterocycles,
dialkylsulphides
4
for
[228].
metalloimmunoassay
or HClO
acid
Drug derivatives,
[227].
to form haptens which were in turn treated
with bovine serum albumin
with
with metallocenes
bound to a solid phase substrate,
Ferrocenyl-
CH2CH2SCH2,
by the esterification
of
and (+)-2,2-dichloro-l-methylcyclo-
acids with the appropriate
(13.10) showed
insecticidal
ferrocenylalcohols.
activity
against
house-
flies [231-J. The E-nitrophenyl (13.11;
ester of (E)-ruthenoceneacrylic
M = Ru) was shown to react
p-cyclodextrin,
but with a poorer
in a complex
binding
acid
to acylate
and rate constant
than
e
/
0 M
6
0
0
qfC0~~N02
0
0
Fe
6 0
0 *02
13.12
13.11
13.13
for the corresponding The cyclopentenyl an excellent
ferrocene
ester
substrate
The effect of pressure E-nitrophenylesters P-cyclodextrin
compound
(13.11;
(13.12) was prepared for the cyclodextrin on rates
and found to be reaction
of transacylation
(13.11 and 13.13)
was also investigated
M = Fe). [232].
of the
in the presence
of
[233].
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