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Ferrocene
163
ANNUAL
SURVEY
GEORGE
EARR
Department
COVERING
THE YEAR
and BERNARD of Physical
Wolverhampton,
WV1
1978+.
W. ROCKETT Sciences,
ILY
(Great
The
Polytechnic
Britain)
CONTENTS 1.
Revieus
2.
Structural
3.
Stereochemistry
4.
Spectroscopic
5.
Reactions
6.
Ferricinium
163 164
determinations of ferrocenes
166
and physico-chemical.
studies
170 175
of ferrocene salts
180
carbenium 7.' Ferrocenyl Ferrocene chemistry 8.
ions
186 160
(i) Photochemistry (ii) Derivatives (iii) Complexes (iv) General 9. 10.
Biferrocenes,
11.
Applications
metals
(metalloids)
202 208
ligands
chemistry ferrocenophanes
Ferrocene-containing
and annelated
219
ferrocenes
227 230
polymer-s
of ferrocenes catalysts
(ii) Ferrocsne
stabilizers in analysis
(v) Biochemical
230
and photosensitizers
(iii) Ferrocere (iv) Combustion
1.
other
of ferrocene-containing
(i) Ferrocene
12,
containing
190 193
232
and improvers
233 236 237
control and biological
applications
238
References REVIEXS Sutherland
and co-workers
have
presented
a review
hydrogenation of aromatic ligands during exchange ferrocene and arenes in the presence of alumkum .mechsnism
of the.hydrogenation
applications.
were
considered
*Ferrocene, AMual metal. Chem., 167
Surve (1979
was
discussed
on the
reactions chloride.
between The
and the synthetic
.[I]-
covering iAL year 1977 see J. Orgznop. 53-I-54.
164 The applications
of
(T-cyclopentadienyl)transition
complexes Solomatin
have been discussed by Kochetkova has revieued the use of ferrocene
chemistry
[3].
of the 1976
Ferrocene
literature
The chemistry
[41-
in a wider
review
STRUCTURAL
2.
Tne
have
been
mixed
each
the application out for
complexes
ligands
a good
linear
the charge density evidence indicated character X-ray
rings
structure
density
from
analysis. from
carried were
ring
proton
out..
found
in
proton,
on the free
level 2g levels having
was
ligand,
change
in
and there ionization
_ The crystal
groups
the y-cyclopentadienyl
(71.
studied
degree
by ultralong-
of delocalization
was an appreciable energies
and molecular
and decamethylferrocene
In both molecules The methyl
formation
was a high
for the e
50 kJ mol -' [S-J.
staggered.
Calculations
also
the corresponding
of ferrocene There
of sgm-octamethylferrocene
deviated
were
for a given
on complex
approximately
uere
such as ferrocene,
on that proton. It was concluded that the an appreciable diminution in the aromatic
in energy
X-ray
with
(T-hydrocarbon)
formation
the appropriate
correlation
approach
complexes.
snd C7H7+ shift
were
orbital
metallocenes,
on complex
3d population
by
included
SCF x0 calculations
diemagnetic
C6H6
order
spectroscopy.
of electron
INDC
and half-sandwich
for
of the ligand
The electron wave
[6].
including
The 'H ?7PiRchemical
to the shift
compounds
of the molecular
several
CsH5-,
in then--bond
case.
complexes
has been
[s].
and related
considered
complexes
sandwich
showed
was
metal
Reductions
in a review
and 7-arene
ferrocenes
and Kowarsch
of ferrocene
carried
for the free
relative
of q-cgclopentadienyl
by Volz
compounds
transition
included
DZTE~~IINATIONS
and
to these
has been
of heterocyclic
structures
discussed
chemistry
metal
and Krynkina [Z]. compounds in analytical
were
the
structures determined
-cyclopentadienyl ? in z-octemethylferrocene ring plane
being
of
rings
inclined
away
the iron atom.
determination temperature The
High thermal motion prevented an accurate of the geometry of decamethylferrocene at room
[9].
structure
of 2-silver(dimethyleminomethyl)ferrocene
(2.1)
The silver atoms formed a was investigated by X-ray analysis. planar square with the substituted ?-cyclopentadienyl rings acting as bridging ligands through one of the carbon atoms Of each ring. The nitrogen
atoms
did not
appear
to participate
in a distinct
165
Fe
2.1
2.2
coordination (2,1) were
of the silver also
atoms.
investigated.
of the Complex
Some reactions
Thermal
(2.1) and cymantrenylsilver
cp~trenyl derivative (2.2) and symmetrical-radicals PCIThe crystal
and molecular
of the complex
decomposition gave
the coupling
structure
of a mixture
the ferrocenyl-
products
of
of ferricinium
tetra-
chloroferrate was determined by X-ray diffraction. The q-cgclopentadienyl rings were almost eclipsed and nearly parallel. The inter-ring
distance
of ferrocene. does not
X-ray
chanels
x which
concluded
diffraction on cooling consisted
of channels enclosed
study
bond
of three
density
were
The crystal (2~5~ K) phases
structures in ferrocene
[II]. to a single-
with
7 and 32.
rings
were
delocalised
of the ordered determined
were
temperature
formed
a
of 120°. Within
occupied
the iron atoms were
which
a pitch
32 were
in
transition
At the higher
molecules
syrmnetries 3,
around
of an electron
subjected
phase
to 100' K.
of thiourea
d?mensionally
observed
was
to that
at 29s" K and the changes
channels, sites of point symmetry iron atoms. The ?-cgclopentadienyl regions
distance
a reversible
dotm
identical
the removal
clathrate
by spiralling
point
is almost
that
the Fe4
that accompanied
also
the structure honeycomb
3-36
thiourea-ferrocene
reflections observed
It was
seem to affect
A 3:1 crystal
was
The
these
by the ferrocene
disordered
and
cyclopentadienyl
electron
[12]. (IsO
K) and disordered
by K-rag
The structure .of the ordered phase was triclinic sixteen molecules in the unit cell on noncentred
with
crystallography. eight
sites-
The
of the
166 structure
the disordered
of
phase
was
found
that proposed in previous models [13]. of the mesophkse fqrm The structure
of
to
be
different
from
formylferrocene
(44-123" C) has been examined by Fioessbauer spectroscopy and-X-ray diffraction . The phase was found to consist of an orientationally disordered orFented
molecular at
mass-iron 3.
random
of 46 pm
STEREOCHHMISTRY A new method
absolute
through
of mass
on average, .~ with a centre of
[14]_
developed
assigned
for the determination
and optical
purity
stereorelating
The absolute
alkylferrocenes. (3.1) was
contres
were,
OF FHNEIOCENES was
co_nfiguration
derivatives
their
about
distance
The molecules
crystal.
of chiral
metallation
configuration
of the ferrocene
of ti-dimethylaminoof the aminoferrocene
[lS].
Fe
*
0 3.1
Cyclisation of g-ferrocenyl-a-phenylbutanoic the exo- and endo- -phenylferrocenocyclohexenones (3.3 and 3.4) were
The ketones
used
1,4-diphenylferrocenocyclohexenes absolute
and relative
to prepare
acid (3.2) gave (3.3 and 3.4). the pseudoasymmetric
(3-5, 3.6 and 3-7) and compounds
the
stereochemistries
of these
were
(3.8) was
by active ti-phenylethylamine The ketone (3.9) was treated
determined
c4. The racemic
and cyclized -Ath
phenylmagnesium
reduced
The
acid
to give
to
the
synthesis,
the ketone bromide
ferrocenophane
relative
resolved (3.9).
to give
the alcohol
(3.1-l) with
and absolute
retention
configuration
(3.10) which of
was
configuration.
and conformation
167
CH2CE2CO2H
0
Fe
0
3.3
3.2
3.4
Ph
Ph
Ph :
““3
:
0
Ph
Ph
3.5
of some methyl described.
substituted
The circular
carbocations were Fermentation glucose
solution
(+)-alcohol Treatment aluminium This
3.7
3.6
amine
curves
of various
reported [17]_ of ferrocene aldehyde-d resulted
(3.12)
was also
[3)-_(l,lf)-ferrocenophanes dichroism
with
in stereospecific
together
with
a small
metallocene
bakers'
reduction
amount
yeast
in
to give
the (3.13).
of the ether
of the alcohol (3.12) with bis(dtiethylamino)methane chloride gave (+)-N,N-dimethylaminomethyl-Id-ferrocene. readily
formed
a palladium
sodium tetrachloropalladate It has been shown that
complex
[IB]. the non-Saytxeff
on treatment dehydration
and
with
of
W-
ferrocenyl-t-carbinols to ferrocenglolefins is subject to stereochemical control in non-acidic media and in acidic media under Specific catalytic effects were not implicated kinetic control. Thus 2-ferrocenylin the determination of product stereochemistry. 3-methyl-2-butanol underwent
had
dehydration
the preferred with
neutral
conformation alumina
(3.14)
and
to form predominantly
3.8
___ --: c 3.9
H
1 :
I
:
H
I I
me_
---
Ph
3.11
!-
oI
0
H
Fe
Fe
I
0 *
3.12
3.13
OEG
169
-H20 Fe
3.14
the ferrocenglolefin acid under 3.16) with Cl9
3.16
3.15
kinetic
in which dilute
(3.15) while control
gave
dehydration
a mixture
(3.15) predominated.
hydrochloric
caused
with
trichloroacetic
of the olefins
Treatment
rearrangement
(3.15 and
of the olefin to the isomer
(3.15) (3.16)
I* The
(dimethylamino)methylferrocene
to the corresponding the dimethylamino formic
primary
group
with
was converted
(3.17; R = H) by displacement of SCH2C02H using thioglgcollic acid and
acid
as the reagent followed by treatment with ammonia, chloride and mercurg(II) chloride to form the product.
ammonium
The ferrocenylbutylsmine in asymmetrically
CHNR2
I
CHkIe2 Fe
3.17
References
(3.17; R = Ke)
amine
p_ 238
induced
(3.17; R = H) was used synthesis
[20].
as a chiral
template
170
4.
SPECTROSCOPIC
AND
orbital
A =olecUlW
carried
PH!fSICO-CHENICAL
and
(CNi30 and INM)
some
A semi-empirical was applied
molecular
to ferrocene.
the photoelectron
ionization
between
orbital
was
ferrocenes.
calculated
method,
p_
and
the PEEL method,
A consistent interpretation of both spectrum and the absorption apectrnm
The calculated
obtained.
calculations)
substituted
agreement was obtained spectra [21].
satisfactory
experimental
were
study
out on ferrocene
STUDIES
order
of the highest
occupied
(02,) ionization potential (a,g), orbitals, ionization potential agreed with experimental assignments in photoelectron spectra S.nd
the calculated electronic
The
and trimer
were
INDO series
structures
than
structures
orbital
molecular
molecular
bonds.
between
the metal
2px2pg
orbitals'of
INDO
transition
SCF
MO
metal
were
calculations sandwich
and the trimer StrUctUres
were
studied
orbitals
the major
Out
for
but
and the
contribution
significant
end the carbon
of the ligands carried
out
including
for
interactions 2s and
a series
of one extra
ligand
to the
[.2&j.
ferrocene
cobaltocene
in a dominantly
stable
was used
except
carried
bis(q-benzene) In all these complexes.
them by the addition
to reside less
were
complexes
its dimer orbital
ferrocene,
were weaker,
the 6-frameworks
The self-consistent method
made
[22]*
of the dimer
3d, 4s and &I orbitals
systems obtained from For all the complexes was predicted
rings
There
ValUeS
head-to-tail
calculations
including
of the ligand
metal-ligand
orbital
a Hueckel
and for some mixed sandwich the interactions between the metal
T-orbitals
generated
to the observed
the corresponding
of metallocenes,
complexes compounds
close
of ferrocenylacetglene,
using
head-to-head
stable SCF
were
calculated
me
treatment.
vere more
a
energies
the
level
of
electron.
extra
electron
and the species
than
the corresponding
d6 complexes
charge
and configuration
molecular
to compare
the electronic
(7-cgclopentadienyl)-(3)-7,2-dicarbollyliron
d6
and for
structures
and ferrocene,
[251. of
It
was concluded that the iron atom could bond to the open nearpentagonal face of the carborane in a similar way that it could bond
to
of.the seme dienyl r;llg WI-
were
ring except that the interaction However, these 6-orbFtals of the dicarbollide. the r-orbitals of the cgclopentasymmetry type as
a cyclopentadienyl
involveds-orbitals
171
A thermodynamic study of ferrocene were
obtained
the vapour
for
of temperature [27]. phase
of ferrocene
the Willis
wes carried
out. Equations as a function
of ferrocene
Molecular configurations in the disordered have been examined and interpreted in terms of This model
model.
an antiprismatic
pressure
molecule
permitted
of D
permitted
for the prismatic r _ independent 1281.
only one orientation for The two orientations
symmetry.
Sd molecule
of Dsh
symmetry
were
were investigated. Irradiation of ferrocene at doses of <2 x 10 15 protons gave only lattice defects but at doses of 2 - 5 x 10 15 protons polyferrocene At even higher doses metallic iron and Fe C were was formed. 3 Proton
radiation
formed [Zq]. Ferrocene
was
effects
suspended
in ferrocene
in epoxy
resin
and irradiated,
using
Moessbauer measurethe Van de Graaff accelerator, with protons. ments were carried out on the ferrocene sample after irradiation. It was
concluded
approximately behaviour
that
Fe3C was formed
100 g in size
and these
as ultrafine showed
particles
superparamagnetic
[3Oj.
Ferrocenyl-41-methoxganiline, ferrocenyl-&I-butylaniline, and dibenzyl-I,1 r-ferrocenedicarboxglate 191 I-dioctanoylferrocene were introduced into the smectic B liquid-crystal phase of z;b;;oxybenzylidene-bl-octylaniline.
These
systems
Fe Noessbauer spectroscopy at 'j'705;[31]. of human serum albumin with ferroceneFe and was
investigated A Hoessbauer
.ferrocene
Referencesp_ 238
by Moessbauer study
derivatives
was
[33].
spectroscopy
carried
were
studied
The interaction some iron
complexes
at 8.5 and 300° K
out on tetramethylene
[32].
bridged
Me
Fe
Fe
0
0
0
0
4.2
*
4.3
The fer?ocenophane
peroxides
0 4.4
(4.1; R = H, Me) have been
Fragments investigated by electron-impact mass spectrometry. were found to arise by thermal decomposition, rearrangement or loss of ethylene by a retro Diels-Alder reaction. The results obtained
were
sensitive
mass
spectra
to
the
temperature
of
the
inlet
system
r341. The (4.2,
4.3
and 4.4)
wex-e recorded
in the methylferrocene metal-ligand
bond
of methylferrocene spectrum
(Scheme
4.1).
and its deutero analogues The main fragments and inttirpreted.
formed by breaking of the
were It
was
shown
that
the
ions
C.,,H,,Fe+,
C6H6FeC, C5HSFe+ and C5H6Fe+ originated from a&isomerized form of the molecular ion in wnich all the hydrogen atoms were redistributed among
the ligends[jS].
C6H6Fe+
Scheme 4.1
173
Mass spectrometrg was used obtained from the electrochemical results
showed
present
could
that
to analyse
the concentrations
be determined
the product
alkylation
of
mixture
ferrocene.
The
of the alkylferrocenes
semiquantitatively
using
this
[36].
technique The
electronic
spectra
of two
series
of metallocenes
(M = V, Cr, Mn, Fe, Co, Ni) were (y-CSHS12M and (T-CSH4Me)2M For the V, Cr, Nn and Fe recorded between 10 and 50 x IO3 cm". derivatives
the charge-transfer
bonds
corresponded
only
to
) and for the Co ligandemetal excitations (e2n8 eig 2g' al& derivatives evidence was also found for metalyligand (e 1ge2u) me paramagnetic susceptibilities of these compounds transitions. were
also I,1
determined
and discussed
v-Di(chlorocarbong$
tetramethylpiperidin-4-01 (4.5) which were
was
consistent
internal
the
the two nitroxide joining
kcal mol
groups
the ground
were
with
2,2,6,6-
the ferrocenedicarboqlate The results
investigation.
with an activation energy -1 and with a conformation twisted
in the molecule
excited
condensed
to form
of a low frequency
and first
for the complexes
was
of an ESR
a species
C2
the two groups
The detection
N-oxide
subject
with
movement
[37].
errocene
out of the line
[38]. vibrational
electronic
[Ferricinium]fX-,
slightly
for in which
states
where
has
mode
coupled
to
been reported
X = tetrafluoroborate
and
The frequency of the mode in the ground state hexachloroferrate. was -84 cm -' and it was assigned to the y6 Raman inactive ring Intensities were discussed in terms of the torsional vibration.
Fe
4.5
Frank-Condon
factor
in the relationship
for the Raman
process
r393TheTf-electron density at the $-carbon chalcone
(4.6) was
and the‘value ferrocenes
determined
obtained
atom in the ferrocenyl13 C NMR shielding constants [ho]. NBB data for a series of
from
the
was 0.9297
and M-ferrocenylcarbenium
suggested
that
ions were
discussed. It was ion the cgclopentadienyl
in an oc-ferrocenylcarbenium
ring formed a fulvalene with the W-carbon atom which bonded to the iron atom via all six carbon atoms [4d Ferrocenes CEO,
CO$e, the first
bearing
electron
COMe underwent
one-electron
withdrawing
polarographic
step gave
groups
reduction
a radical
anion
in turn was such
while
the second
Controlled potential two-electron step gave a dianion. at the potential of either the first wave or the second cleavage iron. salts was
of the metallocene
group
The cyclopentadienide to form
applicability
The kinetics acid
in moderately
in the early
stages
A cell has been (633
efficiency
run)
caused
anions
transition
and metal
and tine reaction
of the protodeboronation that
sulphuric
the reactlon
of the protodeboronation which
in an ethanol achieved
of ferrocene-
acid were probably
proceeded
and that there was no indication in the electrophilic attack by a proton
to electricity
of 25 was
compounds
concentrated
described
semiconductor
of light
with
electrolysis wave
[42].
and mechanism
It was concluded investigated. by an 4 - E& 2 - type mechanism that the iron atom participated
based
combined
(T-cyclopentadienyl)metal
of general
boronic
to cgclopentadienide
anions
as CO2E,
in two steps,
employed
solution with
[a].
[43]. an n-type
silicon-
of ferrocene.
an output
Conversion
of 0.25 V and an
Ferrocenyltrichlorosilane
(h.7) was prepared by the addition of lithioferrocene to an excess of silicon tetrachloride. The ferrocenyl-silane (b.7) was attached directly
to a pretreated
platinum
platinum
electrodes
characterised
it was concluded hydrolysis
electrodes
thousand
100 mVs -' with material
that
ferrocene
of the silicon-chlorine
were
five hundred only
The derivatized by cyclic voltammetry aad
the electroactive
of one or more
derivatized three
were
electrode.
very
durable
cyclic
approximately
was
attached
The and in one experiment
voltsmmograms
via
bonds.
were
run
over
at
30% loss of the electroactive
[45].
The ferrocenyl-slime 1,l '-dilithioferrocene
(4.8) was prepared
to silicon
by the addition
tetrachloride.
An n-type
of
silicon
175
0
COCH=CHPh
0
SiCl 3
0
Q-l
0 Fe
0
*
lC1
0
Fe
W
'9,,
0
4.7
4=6
electrode and
to
was
treated the
dipped
with
silicon
the
into
photoelectrochemically
without which
5.
led
showed to
no
a rapid
REXCTIONS
OF
Electrolysis cgclopentadrene
of and
o*o ago 5.1
Refezencesp.238
sodium
hydroxide,
which
surface
became
attached
reduced
and
waves
decline
of
and the
covalentlg ferrocene
oxidized
Whereas
deterioration.
cyclic
washed,
a build
dried linked
was
forms
nonderivatized
up of silicon
photocurrents
cycled
repeatedly
dioxide
C461=
FEBROCBiGS
+
Fe
(4.8)
The between
any substantial
electrodes
aqueous
silane
surface.
4.8
a solution lithium
containing
bromide
between
dimethglformamide, an iron
anode
and
a
176
nickel
cathode
gave
ferrocene
in a current
yield
of 88%
‘[43’].
A series of labelled
ruthenocenes was prepared by heating ferrocenes with '03Ruc1 . For example, benzoylferrocene were heated at 180~ ro2 anproximately half an hour to 3 give benzoylruthenocene, ruthenocene and I,? *-dibenzoylruthenocene. -M'nena mixture of acetylferrocene- 59 Fe and ferrocene methylcarsubstituted and '"?RnC1
boqlate
was heated
of labelled
The ligand ferrocenes
with
dimethylferrocene derivatives isolated
in the presence
ferrocene
derivatives
exchange coronene
of iron(II1)
chloride
obtained [&a]. ferrocene and some substituted reactions of Ferrocene and l,l'were investigated.
underwent
(5.1; R = H) and
exchange
to give
the ?-coronene
(5.1; R = #e) respectively
as their hexafluorophosphate
salts
which
[49].
.+
Fe
2-k
5.4
a VaI'ietY
was
were
177 Ferrocene
underwent
dimethylanthracene aluminium
mixture
hydrogenated and
endo.
was
used
(5.2
and
ligand from
in in
in
the
5.4)
exchange
(5.2)
and
form
where
the
aluminium. at
an the
ligand
were
exchange
had
The
obtained.
between
the
underwent
The
and
reaction
i-
reflux
cation
ligand in
two
reactLon,
(5.2) excess
been
with
9,10-
added
(5.5) and
was
products formed
ferrocene
or
of
by directly
[SO].
wit‘n phenanthrene
presence
aluminium
Q
and
chloride
9,10-dimethylphenanthrene gave
the
mononuclear
+
0
&
5.6
-I-
Fe
cis
(5.3)
isomeric
ferrocene
exchange
the
temperature
dication
Fe
p_ 233
with
chloride-
stereospecifically
hydrogen
0-O
References
reaction aluminium
cis-9,10-dihydro-9,10-dimethylantbracene
9,10-dimethylphenanthrene
cyclohexane
of
to
9,10-dimethylanthracene Ferrocene
exchange
presence
decalin
product When
a ligand
the
in cation
(5.6)
1'78
.Q .A3
Q 0
co ‘CH2 +&co-
Fe
CO(CH )
0
0
Fe
Fe
0
A’
0
n
5.11
5.12
CO (CH2)4C02H
Fe
Fe
Fe
CO (CH2 14C02H
5.14
5.13
Fe
Fe
Fe
24
co
H
2
179
and the binuclear products addition, were
(5.7).
cation
vlalogous products
Exchange
to those .obtained with where
the mononuclear
hyorogenation
cation
(5.8)
with
phenantbrene
phenanthrene
accompanied
gave
but gave,
exchange,
these
dication
(5.9)
and the binuclear
CN* A series possibly
by treating presence istered
with
ferrocene
to rata
C
with
l-4
(5.10; R = CS_7 cgcloalkenyl
al%&
Ph, CH2Ph,
the appropriate
acid
Cl) was prepared chloride
Some or' the scylferrocenes
of a catalyst.
Ferrocene presence
of acglferrocenes
substituted
were
acylated
of aluminium
with
chloride
isononanoyl
to give
chloride
Fe
0
in the
Fe
0
I Fe
0
.*_
admin-
(trimethylhexanoyl)ferrocene
153 I-
5.16
in the
[.52]. was
*
5-n
0 5.18
180
Femocene the.presence
alkylated with methylmonochloroacetate
was
of aluminium
chloride
to give methyl
in
ferrooenylacetate
The acetylation of ferrocene with acetic anhydride has been [%]reported using as catalyst magnesium haiides (chloride, bromide and iodide)
in the form
of the etherates
The Friedel-Crafts has
been
methylenedichloride reported 5.13)
together
with
formations
using
In addition
four
(5.14 and 5.15) secondary
The reaction
of ferrocene
in the presence
ferrocenylalcohols
monoacylated
which
compounds with
predominant,
chloride and
(5.12 and
were
arose
obtained
by trsns-
[56].
1,6dioxaspiro[&&]nonane
of trifluoroacetic
(5.17 - 5.20)
adipoyl
as catalyst
to the previously
ferrocenes
products
formed
[ss].
with
chloride
(s-11), both
product
of the first
(5.19) was
of ferrocene
aluminium
as solvent.
polymeric
and diacylated
(5.16)
acylation
reinvestigated
in benzene
acid
in which
the mechanism
gave
a mixture
the binuclear
of the reaction
of
diol was
discussed
c-5.71. 6.
F'EIEzRICINm The
SALTS
crystal
and molecular
tetrafluoroborate
(6.1) has been
The diferrocenyl
cation
has
determined
for diferrocenyl
were
to be bent
found
the two iron and 2.81
atoms
stabilization interaction
ketone.
It was concluded
from metal-exocgclic
and to delocalization shifts
spectroscopy.
Shifts
ion have of both
that
carbon
distances
reduced
the distorted and that
attributable
charge
been
determined
by 1%
and negative
to such
[58].
perdeuterometallocenes
positive
rings between
to 2.69
interaction
ions was
of positive
in paramagnetic
the perdeuteroferriciniu
were
that
to
ferrocenyl
so that
carbon
crystallography. similar
substituted
atoms
of CGferrocenylcarbenium
Isotope
by X-ray
conformation
The
and the exocyclic
resulted
of o<,oc-diferrocenylmethylium
determined
a transoid
at the &-carbon
g respectively.-
structure
structure
including NMR
sign were
observed
and a large dipolar shift was observed for the perdeuteroferricinium ion. The isotope shift increased with the number of unpaired electrons and with the efficiency of electron delocalisation LWThe mixed valence cations of biferrocene and biferrocenylacetylene (6.2) were formed from the neutral ferrocenes using [(2,2~-bipyridine)2Ru.PPh3.C1](PF6)2 cations
displayed
to intervalence
near-infrared transfer
as the oxidiaing
absorption
transitions
bands
between
which
isolated
agent.
The
were
assigned
Fe(II)
and
181
Q
+
0
Fe
0 0
CH 4
0
0
BFk-
Fe
~
0
~
6.1
Fe(III)
sites.
4.2
The energies
functions
of the dielectric
with
theory.
Hush
iron separation valence cations transfer
optical
6.3
constant
The energies
in the cation. have localized
properties electron
of these
were
transfer
were
were
correlated
of the medium also
It was valence
consistent [60].
bands
concluded sites
with
used
correlated that
with
in accordance
with
the iron-
the mixed-
and the intervalence
the Hush
treatment
for
182
of the neutral
-_-Oxidation
benzene
while,
both
atoms
through
ferrocenes
Q
indicated catalyses
me
of native initial
state.
strong oxidation
Fe+
rates
CH2CH2R
6.5
BF -.
4
6.6
atoms
ferricinium
and maximum
that the two iron electron
in the cation
The magnitude
r611. of ferrocene
or immobilized
iodine. in
in intramolecular
interactions
T-system
with
and the averaged-valence
indicated
the two iron
0
6.4
(6.2)
involved
oxidation
to the corresponding
in the presence studied.
in contrast,
the conjugated
The enzyme
cation
spectroscopy
(6.2) were
in the same
rupole.splitting
ferrocenylacetylenes
valence
Moessbauer
in the cation
transfer were
the mixed
(6;3).
cation atoms
gave
between and
(6.3)
of the quadthe iron
some
substituted
ions by -hydrogen peroxide
horseradish of oxidation
peroxidase were
was
determined
133 and It was found hydrogen
that
peroxide
the rate
of oxidation
concentration.
horseradish
peroxidase
the absence
of any added hydrogen
A series were
ferrocenes decrease
in a coupled
system
peroxide
Compared
the infrared
intensity
glucose
by
otidase
in
[62]. and their
to the analogous
spectra
of the
also oxidized
hexafluorophosphates,
(n = 0 - 5), was prepared
recorded.
in band
was with
of sgm-polymethylferricinium
(Me,C5H5_n)2FeefPF6spectra
was independent
Ferrocene
of the salts
displayed
for C- H stretching
infrared
sgm-polymethyl-
modes
a marked of the methyl
Whereas, the intensities and the frequencies of the groups. corresponding bands for the ring M stretching modes were higher
[631The reaction with
of sodium(dicarbonyl)(I_cgclopentadiengl)ferrate(-l)
the ferrocene
derivatives
(6.4; R = E-MeC H SO , Cl) gave
2-ferrocenylethyldicarbonyl(?-cyolopentadienyl(i~on3(6.~). of the latter ferriciniura Reaction gave
compound
salt
(6.5)
with
Reaction
salts
of the dicarbonyliron the cationic
released
from
the complex
hydroxide
(6.7) with HBF4 or Et30BF4 R = H and Et) respectively. (6.8;
(6.8; R = H) with diazomethane gave the methylated derivative (6.8; R = Me) [6S].
gave
iodide,
sodium
or sodium
complex
complex (6.10).
(6.9) with ferrocenylFerrocenylethylene was
(6.10) on treatment
trlfluoroacetate,
borohydride
sodium
with
triphenylphosphine,
cyanide,
sodium
[66].
BP -
Fe
4
6.7
References
the
salt
ethylene sodium
gave
of the ferrocenyl-ketone
of the
corresponding
tetrarluoroborate
[64].
the tetrafluoroborate
Treatment
trityl
Treatment
p_ 238
6.8
+Q
184
Q 0
Fe-l/ (co)2
f
0
Me C2
BF
4
-
2
zh,
CH2
iCH
0 0
BF -
4
Fe
6.9
*
0
6.10
Oxidation gave The
the
reaction
presence
of
ferrate(II) being
of
the
corresponding
formed
of
the
potassium and
the
borinato-iron
complexes
ferricinium
derivatives
ferricinium
hexacganoferrate ferricinium
[68].
Q 0
Fe
6.11
ion
6.12
ion
with
(6.11;
hydroxide
gave
R = Me,
(6.12) ion
potassium
decomposed
without
Ph)
[67]. in
the
hexacyanoany
ferrocene
185
6.13
The
thermal
ammonium and
decompositions
perchlorate
and picrate
ethylenediferriciniu
The mechanisms Complexes transition
ion-ferrocene
p-diketonate
cyanide, changed
system
were
acetone,
and
(6.13)
[TO]
isopolgacid
determined varied
of the acid
and the quantity
were
studied.
anions.
cation
and
Amino-
in some acidic
betueen
(hydrochloric, of the organic
solvent
dimethylformamide
alcohol,
aqueous-organic
+O.l - to.66 V as the sulphuric and perchloric) (acetic
and
acid,
methyl
dimethylsulphoxide)
[72].
Cyclic of oxidation organic
and I,1 I-diethylferricinium
in complex formation with transition The electrode potentials of the ferricinium
The potential
concentration
[69]
perchlorates
ferrocenes also took part metal thiocganates [71].
changed
(ferrocen~lmeth~l)dimeth~l-
of the decompositions were discussed. have been formed between the ferricinium
metal
solutions.
of
voltannetry
solvent
perchlorate. the reaction
has been
of ferrocene mixtures
Rate was
containing
constants
found
used
to investigate
to the ferricinium
acid-
0.02 fi tetraethylammonium
for the oxidation
to involve
the mechanism
ion in aqueous
a fast
were
protonation
obtained step
and
followed
by a change from solvated ferrocene to hydrated ferricinium ion. The instability of the ferricinium ion caused the reaction to be Changes in the nature and concentration Of quasi-irreversible. the mineral-acid
and the organic
of the ferrocene-ferriciniu manner.
These
Refereneesp.238
controlled
solvent
ion couple changes
caused
the redox
to change
together
with
Properties
in a controllable
complexation
of
186 meta-l cations oxid+
formed
the presence
in
Denisovich
of a second
in anode
the ferricinium
of a method
co-workers
and
formed
radicals
the basis
potassium
that
decarboxglation
one
the interaction of carboxglate
the same electrode
at
of dkylfsrrocenes.
formation
deteddng
[73.].
found
generated
iOn
fop
led
of anions
with
to the
For example, the electrolysis of a
acetate,
acetic acid and ferrocene gave a mixture of methylated ferrocenes. A similar reaction of the or their ferricinium ion with radicals generated from dibasic &ids nzitiure
half
of
esters
It was
gave
shown
esters
of ferrocenyl
that the orientating
the same for radical electrophilic
substitution
substitution
containing
effects
in the ferricinium
of the corresponding
derivative c741The ferrocene-ferricinium
cerboxylic
cation
system
function mixtures of
was a better
standard
proton
have
galvanic
mange2
been
in
determined with
cells
measure
has been
little
ratio
effect
alcohol
7.
PRRROCEXYL CARBENIUM IONS The alcohols (7.1; R = 11, Me,
heterolysis acid
(exo-departure
to give
the
ol' the
the corresponding by rotation
diastereoisomer
equilibrium
mixture
exo-protonation
alkylium base
ions which
to form
isobutyl [7s].
Ph) underwent which
and
7.3)
underwent
[76]=
stereospecific
equilibrated quenched
with
bond.
its
When
aqueous It was obtainedunderwent prefer-
wwe
(7.2 and 7.3)
3-n trifluoroacetic
on
OH) in trifluoroacetic
the ferrocenyl--Ci
of the cations-was
group
acid
with
to give ferrocenyl-
exo-deprotonation
in the presence
of
[77].
Ferrocene acid
measurements electrodes.
affinity
protonated
cation
about
sodium carbonate the alkenes (7.2 shown that the alkenyl-ferrocenes ential
function
proton
[75].
and water-ketone
or in the hydrocarbon
on‘the
the
to deter-
end The Pleskov
of the solution
of water-alcohol from acidity
ferrocene
used
platinum-ferrocene-ferricinium
the water-alcohol had
of the acidity
affinities
were
ion as for
neutral
mine Hemmet and Pleakov redox functions in propanol-water iso-propanol-water mixtures containing perchloric acid. me
acids.
of the substituents
was
as a stable
with
isobutyraldehyde
I-ferrocenylisobutanol
carbenium
The
treated ion
which
gave
and trifluoroacetic the ferrocengl-
the reaction conditions used ion..(7.5) was obtained ferrocenylbenctrotrenylcarbenium violet-blue
(7.4)
under
fluoroborate.by
treatment
of the appropriate
Q 0
ccc
I:
0
NPh 'Me
Fe
Fe
0
7.1
7.2
Fe
7.3
Fe
7.4
carbinol
7.5
with
fluoroboric
acid in propionic
Treat-m-at of ?,3-diferrocenylallgl 3-ferrocenylallgl gave
the catFons
(7.6) with
alcohol
with
(7.6 Pnd 7.7)
N,N-dimethylaniline
(7.7) underwetit a skilar
alcohol
ffuoroboric
anhydride
and I-methyl-1-c~~trenylacid in acetic Treatment
respectively. gave
reaction
[79].
the olefin
snhydride
of the cation
(7.8), the cation
[SO].
A
mechanistic study was carried out on t&e fragmentation of ferrocenyldiarylmethylix~m ions in aqueous acidic methyl cyanide. For example,
the cations
the corresponding formation
References
p. 238
orthe
fulvenes
(7.9; AZ = Ph, E-anisgl) (7.10)
alcohol. precmsors
tog&Aer (7.11).
wFth
fragmented repeated
to give
reversible
-Changes in acid
strength
188
7.6
Fe
*
7.7
Fe
1,
0
0
7.8 and substituent amino)calicene form
effects (7.12)
the dicyclopropenium
potassium
were
investigated
was heated complex
with
[al].
iron(Iii)
(7-33) after
s,&Bis(diisopropylchloride
in
the addition
THF to of
perchlorate
[a23. The acid-catalyzed hydration of ferrocenylacetylenes with alkyl substituents in the 2-, 3- or 1’ -positions has been subjected to a kinetic study. The reaction involved the formation of an intermediate vinylcarbenium ion (7.14) and gave acetylferrocenes as the products [833. from
Comparison of the pKR values for the carbenium the ferrocenylcarbinols (7.15; R = H, 1Ge) with
ions derived t'nose for
the
189
Ph OH
7.10
7.9
7.11
N(CHNe2)2 Fe
2ClO N(CHMe2)2
N(CHKe,),
7.12
Q
&CH2
0
Fe
7.14
References p_ 238
7.13
4
-
7.16
7.15
chromiumtricarbonyl demonstrated
complexes
that the ferrocengl
the chromiumtricarbonyl _
group _
(7.16; R = H, Me)
of the carbinols group
was much more
in stabilizing
efficient
the adjacent
than
carbenium
ion [84]. 8.
FERROCENE
CHEXIST~Y (i) Photochemistry
.The unsaturated with
ultraviolet
acids
light
at pH 9 in the presence and the corresponding chemically
reduced
(8.1; n = 0.1 and 8.2)
of wavelength of nitrous ferricinium
back
ions were
to the original
produced
acids.
Q
cdco2H
0
*
0
8.1
were
irradiated
240-250 nm in aqueous solution Photo-oxidation occurred oxide.
8.2
which
It was
could
thought
be
that
Q .Q
cH2c02- : .-
FS
*
CH2CO2-
.hv Fe
0
*
0
0
0
8.5
8.4
8.3
OH-
-/ OH
S%
CH2CO2
I Fe
6 0
8.6
oxidation occurred by electron transfer to nitrous oxide from a photo-excited state of the acid c85l. The photochemical excitation of the ferrocenyfacetate (8.3) and ferrocenoate anions gave, in each case, an excited state (8-k) which
transferred
an electron
to nitrous
oxide
which
acted
as an
electron acceptor. The lifetimes of the excited states were 2ps and O,O?ys respectively. The product of electron transfer from the excited stat,e of the acetate (8.3) was. -the zwitterion (8.5) w?nich with,base
was
thought
(y-cgclopentadienyl)%ron ethanol _ferricinium
to form
complex
the
(a.61
(q-cgclopentadiene)[86].
solutions of octamethylferrocene and octamethylhexafkorophosphate were irradrated with incandescent
192
40-500 u
lamps.
of the solutions absorption
A periodical
variation
was
throughout
spectra
observed
studied
(210-800
increased with the concentration that an oscillating photochemical
in the optical the rsnge
nm).
density
of electron
The period
of variation
of the solution. It was suggested redox process was being observed
Ca7 1. Carbon tetrachloride and other halogen0 compounds with a similar or higher electron affinity underwent photoinduced dehalogenation in A chain alcohol in the presence of ferrocene or iron(iI1) chloride. propagation
mechanism
was used
to explain
the high
obtained which was >6 for carbon tetrachloride. acetate was monodehalogenated in low quantum yield it had a high electron affinity [88]. Copolgroers of methyl ethyl
methacrylate
have
methacrglate
been
photosensitizers acid
evaluated High Red A.
and Fast
methacrylate of Perrin's excFted both
synthesized
The quantum
model
quenching
though
with
l-ferrocenylas
and t-heir efficiencies
low quantum
changes
quenching
ferrocene
interaction
nearest-neighbour
caused
yield
for static
arzd ground-state
even
for the redox reaction between L-ascorbic proportions of I-ferrocenylethyl
in the copolymers
sensitization.
or styrene
quantum yield Methyl trichloro-
yields
discussed
for in terms
interaction between adjacent It w2.s considered that
groups.
and energy
ferrocene
were
groups
migration
with
occurred
the former
between
assuming
more
importance than the latter [ 891. The quenching of [U02]2f emission by ferrocene, some substituted some substituted ruthenocenes and osmocene ferrocenes, ruthenocene, has
been
investigated.
of the excited obtained
both
The values
state from
a quencher, 10%
reduction
by iso-propanol of local
it was concluded
was negligible [913.
within
in the presence
that
quenchers
were k -Q measurements. potentials
transfer
mechanism
[90].
of benzophenone
concentrations
strong
the oxidation
an electron
vinylferrocene-VinylbenzoPhenone
the presence chain
supported
were
constants
and lifetime
with
(U022+)r- and the metallocenes
benzophenone) of
intensity
correlated
and this
The photochemical and
and the quenching
luminescence
k were of loglo--&
of the metallocenes between
All of these metallocenes (U022+)"
and absence
copolymer of ferrocene,
energy
the triplet
and poly(vinyl-
migration lifetime
was
of ferrocene
studied.
In
which
behaved
along
the polymer
(approximately
as
193
(ii) Derivatives Ferrocene
containing
Gas metallated
tetramethylethsnediamine sodioferrocene yields
after
yields
were
other metals
(TZE!DA) to give
in the ratio
(metalloids)
by n-pentglsodium
I,?'-disodioferrocene
The reaction
9:l.
in the presence gave
near
In the absence 1 hour at room temperature. and polymetallation products were also
lower
of and
quantitative of TIGDA obtained
c94* The reaction between a-butyllithium and potassium(-)(lR)menthoxide gave n-butglpotassium w‘hich was used to metallate ferrocene. The
l,lr-dimetallated
obtained
ferrocene
in 74% yield
n-butyllithium
[93].
in the presence
(PICDT) in the molar
ratio
was t'ne predominant
The metallation
both
a dilithioferrocene which was The 'H by 'H IWR spectroscopy and X-ray analysis. was temperature dependent in benzene and toluene solution The solid cyclopentadienyl and base exchange taking place.
I?< :
r-4
-qlpfjj \ :
Fe
Fe
8.8 Fe
8.7
References p. 238
and was
with
of pentamethyldiethylenetrismine
l-3 gave
investigated zII.3spectrum with
product
of ferrocene
194 complex
[(q-CsHk)2Fe.PWT.Li2]2
soloated bound
md
unsolvated.
to the three
lithiums between
(8.7) had two types of lithium The solvated lithium atoms were each
nitrogen
.partTcipated
atoms
of the P&KIT while
in a four-centre
the two ferrocene
electron
atoms
the unsolvated
deficient
briQe
grollps.
The lithium-iron distance was short (2.667 g) which indicated bondin g between the lithium-and a ferrocene e molecular orbital [94]. Phenylgazoferrocene was mercurated to give a mixture of 2-chloromercuri(phenylazo)ferrocene (8.8; X = H&l) and bis(2phenylazoferrocenyl)mercury. by iodine yield
Both
to the 2-substituted
of the compounds
iodoferrocene
were
converted
(8.8; X = I) in high
[S].
ferrocene derivatives (6.10; R = Ne, Et, CN, CONe, trifluoroacetate gave high yields of the corresponding mercurated derivatives (b-9 1. The mercurated compounds (8.9 ) were converted to the halofeProcenes (6.10; X = b, 1) by reaction with potassiti-trdbromide a-?d potassium triicdide / respectively [96]. Treatment
GHO;X
=
H)
of- the
with
me~c~~g(1I)
X
Hg(02CCF3) (F3CC02)Hg
0
* (F3~~02)~g
R
Fe
Hg(02CCF3)
Fe
Hg(02CCF3) 8.10
8.9
The ferroceayldihaloboranes (8. II; K = Cl, Br, I) were prepared with the corresponding by the reaction of ferrocenylmercurichloride The infrared spectra of the ferrocenyl-boranes trihalide. and "E-X (8.11; X = Cl, Br, I) wnre recorded and the 'O-X
boron
stretching
frequencies
were
Ferrocenyldibromoborane
(8.12) to give was characterized
assigned
[97].
combined
with
the
distannacyclohexadiene
the diferrocenyldiboracyclohexadiene as
the
nickel
complex
(a.141
[98].
(8.13) which
195
Q 0
BX2
Fe
Me2Sn
/=l
SnMe2
U
6
0
-
8.12
8.11
The thiodiborolene
(6.15)
was
treated
and bis[dicarbonyl(?-cyclopentadienyl)iron]
with manganese to form
carbony
the triple-
decker mixed metal complex (8.16). This product (8.76) gave a cationic complex with aluminium cbJoride which ~2s in turn pyrolyzed to yield the neutral tetra-decker complex (8.17) [99]. R1R2Si(C=CH) The hydrosilylation of silglacetylenes, 2' uhere R' = R2 = Et Ph R1 = Ne R2 = Ph, with the ferrocenylsijane (8.18) UsingaSpki~r's'catalyst'gave the products (8.19; R1 = R = Et, Ph, R' = Me, R2 = Ph) which were formed according to Farmer's rule
[IOOJ. Reaction of c+naphthylferrocenylmenthoqsilane with boron t&fluoride etherate gave the bifunctional enantiomeric silane Treatment of the ferrocenylsilane (8.20) with palladiutn(II) (8.20). Treatment of the chloride gave the fluorochlorosilane (8.21).
8.13
Refemmsp.238
8.14
196 S
__B’
‘B-
J-4
Et
Et
fluorosilane (8.20) with Grignard reagents and organolithium compounds resulted in selective replacement of the fluorine In these
reactions
there
was retention
of configuration
with
atom. the
organolithium compomds and a mixed stereochetistrg was found When Grigna.rd reagent was used in solvents wTth Grignard reagents. with increasing basicltg the stereochemistry changed from inversion
SLHPhNe
Fe
SiPhMeCH=CH-
Fe
0 0
8.18
_o 0
8.19
SiR'R2
197
Q 0 0
P ---Si----H
Q 0 0
GNP
Fe
7
---si ----c1 a-Np
Fe
0
0
a-Np
= W-naphthyl
8.21
a.20
to'retention. reagent
whilst
attack
[lOI].
acetylene
Inversion retention
was the result of axial attack of the was explained in terms of an equatorial
Monosubstituted
combined
with
acetylenes
trisubstituted
including
silanes
ferrocenyl-
MePhSiHH
in the
presence
ofSpeier's catalyst to give one of two possible regio, where and MePhR'SiCR2=GH selective products MePhR'SiCH=CHR2 *I = R2 = ferrocenyl, R' = cymantrenyl, R2 = Ph, SiPh3 f 102 3 . Ferrocenylacetglene was lithfated and the S-lithio intermediate treated
with
trialkylchlorogermanes
(8.22; R = Me, Et,
Ph) and with
the diferrocenglgermvles (8.22 and 8.23)
(6.23; R -
were hydrogenated
CsCGeR3
Fe
0 0
8.22.
to form
8.23
the germylferrocenes
dialkgldichlorogermanes He,
E-t,
over Raneg
Ph).
These
nickel
to form products
but were
not
198
Q
SiHIqeR
SiMeRCH=CHCMe20H
0
Fe
*
HCGCCMe20H
+
-b
Fe
0
*
8.24
8.26
8.25
reduced
by palladium
powerful
enough
on calcium
to reduce
ti-Hydroxyacetglenes silanes
to form vinyl
carbonate,
underwent
silanes,
hydrosilation
(8.25) to give
the product
reaction
was
the presence
l8.26;
R = Me).
by the nature
of H2PtC16;the
following
with
reaction
with
is
ferrocenylthe
the hydroxgacetylene SimLlar
reactions
The relative
l,l-disilylferrocenes.
determined
which
[103].
In a typical
(8.24; R = 14e) combined
out with
a reagent
silglacztylenes
dimethylsilane carried
0
rate
of the ferrocenylsilane order
of reactivity
were
of the and
was
observed: (8.27; R = Me) >(g.Zk ;
Q
R
=
Me)>>(8.&;
R = Ph)B(8-27
SiRNeR
0
3%
Fe+
SiFIMeR
8.27
8.28
': R = Ph)
[104-j.
199
Complex
formation
investigated. iodide
ions
in ether
x = Cl, Br, I). while
by diferrocenyltin
The dichloride
combined
at -40" to form
A I:? complex
a 1:2 complex
was
formed
Diphenylchlorophosphine presence
with
between
the phosphine
treated
chloride
COBu)
COMe,
(E-30) where
were
the ligand
with
to form
been
cymantrene
prepared
[?Os].
ferrocene
obtained with
(6.28;
in the
ferrocenyldiphenylof benchrotrene
by direct
the loss
together
with
L was triphenylphosphine,
reaction
of csrbcn
analogues
diferrocenylphenylphosphine
diphenglphosphine,
salts
and
dimethylformamide
derivatives
and the complex
The monosubstituted
monoxide. Et, CSH,,,
phosphine
have
with
bromide
dimethylsulphoxide
Ferrocenylphosphine
phosphine [106]a and substituted cymsntrenes
has been
chloride,
the ferricinium
was formed
was
of aluminium(III)
dichloride
with
(8.29; R = h, the benckeotrenes ferrocenyl-
or triferrocenyl-
[107].
Q
:: CH2P~2
0
Mn
(CO)2L
8.30
8.29
A mixture phosphine
of two
oxide
complexes
cgclopentadienyl)iron oxide
(8.31)
Me02CCH2CH2COC1
acid
oxides
with
dicarbonyl(q-
the ferrocenylmethylphosphine
gave
of ferrocenylphosphines
has been
reported.
chloride
using
aluminium
the diferrocenylphosphine
two reduction reduction
products
product
with
and
A typical
of diferrocenylphenylphosphine
in methylene
to give
and a third
References p_ 238
treated
to give
of a number
the treatment
as catalyst
diphenyl(cyclopentadienylmethyl)-
[108].
ferrocenylphosphine
This product
was
dimer
The preparation involved
isomeric
8.31
with sodium
(e-32)
synthesis
oxide
with
chloride in 70% yield.
zinc and hydrochloric borohydride
[109].
-
200
Q
Q0
R2 hHP(O) (OR1)2
0
Fe
Fe
COCH2CH2C02Ne
8.32
8.33
The
condensation
HP(0)(OR1)2
of formylferrocene
(RI = Me, Et, CI-Die2)gave
(6.33; R2 = OIi).
hydroxymethylphosphonates
(6.33; R2 = OH) were anhydride esters
to give
treated
an amine
with
of either
in It'nepresence @4eC6RkNH,
Q 0
ferrocenyl-
phosphonates end acetic
(8.33; R2 = I4e) and
or acetylferrocene
phosphonate
p-02BC6HkNR,
gave
(8.34;
with
the cor-
R' = H, Me;
mor,holino, piperidino; The antimicrobial activity
Bu, Ne2CHCH2). was
investigated
b(O) (OR3j2
R'
[II?].
-e
A2
Fe
2
0
0
8.34
P
kf
Fe
0
T"ese
sulphate
of a dialkylphosphonate
R2 = PhXi,
compounds
ethers
formylferrocene
ferrocenylaminomethyl
R3 = ke, Et, Pr, Ne2CH,
the phosphonates
[IIO].
responding
of al1 these
dimethyl
the corresponding
(6.33; R 2 = COMe)
Treatment
with
the corresponding
8.35
6.36
P
201
8.38
8.37
(8.35) was heated with iron(I1) (8.36) as a stable red
Dimethyl-3,4-phospholyl-lithium chloride solid.
to form
A tetraphenyl-I,1
way
same
the I,?'-diphosphaferrocene
I-diphosphaferrocene
was formed
[112].
A convenient been
reported.
with
1
synthesis of dimethyl-3,4-phosphaferrocene has (T-Cyclopentadiengl)dicarbonyliron dimer was heated
-t-butyl-3,&-dimethylphosphole
(C.37) in 38% gave
carbonyl me
Treatment
yield.
the phosphorus
ferrocene
sulphones
(T-C5H,+CH2)Fe(q-C5H5), prepared
from
the
to give
of
the
complex
the phosphaferrocene
product
(8,38)
with
S02R2
CH2CH2CN,
CH2CR2C02z9
corresponding
sulphonic
0 Fe
0
CR(OH)C6Hq1ale2 3 were
acids.
CHRS-
Y
0
8.39
p_ 238
nona-
[113].
0
Fe
diiron
C8.39; R' = E, Me; R2 = H, Na, Nxt2,
R'
References
in the
2
8.40
Sulphonation
of
-202 methylferrocene lead
salts
combined
with
sulphur
and di-sulphonic
of mono-
trioxide
acids
in dioxane
which
were
Ferrocenylmethanol
[Ilk].
-w%th di-fuxxotional
gave
separated
a mixture as their
and 1-ferrocenglethanol
mercaptana
HSYSH,
where
Y = CH2CH2,
CH2CH2CH2, CH2CHMe, (cH2~H2120, (cH2~H2)2~ to give the corresponding (8.40; R = H, Me) [lls). sulphides Phenylferrocene by aluminium(II1)
treated.with
chloride
(8.41)
c'hromium complex
Cr
Fe
was
and
which
chromium(IIi)
aluminium was
to form
characterized
chloride
the bis(T-bensene)_ -
8.42
Ethynglferrocene was treated with &-PtC12(PMe2Ph)2 the complex trans-PtC1[C=C(C5H~)Fe(C5H5)](PMezPh)2 which in methanol
(8.42) rather ion
than
to give
a plat;inum stabilized
the alternative
ferrocengl
to form underwent
carbenium
stabilized
ion
carbenium
[117]. Diferrocenglme&curg
acid
[116_1.
as the iodide
Fe
8.41
protonation
fo1lowe.d
was
treated
with
MeAuPPh3
the ferrocenylgold complex
in THF to form
and fluoroboric
[(q-CsHs)Fe(y-C,$Q)-
(_LuPP~~)~ ]BF, [I181. 8.
(iii) Complexes
of ferrocene-containing
l,l'-Bis(diphenylp*hosphino)ferrocene bidentate
ligsnd
towards
transition
ligands has
metals.
been
evaluated
Complexes
as a
containing
(8.43; M = CoC12, cobalt, nickel and copper halides were obtained CoBr2, Co12, NiC12, NiBr2, Ni12, GUI) together with three tetraThe ferrocene ligand carbonyl complexes (8.44; M = Cr, MO, W)was found ethane
to behave
[I1 93.
in much
the same way
as bis(diphenylphosphino)-
203
Q\ PPh2
0
!=f
Fe
/ 0
Q 0
I
kPh2
0
Ferrocenoylacetone (8.451, HL, has been used as a bidentate ligand to forx the complexes VOL2, CrL3, EnL2, CoL2, NiL2, Cti2. The complexes were characterized by spectroscopg and the ML2 complexes underwent thermal degradatZon in a single stage remf;ion w%th the exception of CuL2, R 20 which was degrsded by a two-stage process [120f. Titanium polyferroeene oximes (5.46; R = Ph, Ma) were prepared by the reaction of'bis(~-cgclopentadiengl)titanium dichloride with the appropriate oxime in the presence of excess base. The polymers and by (8.46; R = Ph, I&) were malysed therzuogravimetric~J..Ilg
0 0
Fe
n
S-45
iteferen-
p.228
8.46
,
o- P 0
0
Fe
Nb
,*0
0 0
i2
8.47
differential by similar 180~
scanning exothermic
and above
Tine polymers of their
this
began
weight
Reaction
calorimetry. routes
temperature to degrade
up to 600s
Thermal
in nitrogen they
occurred
at about
chloride
by Noessbauer
Q 6:
spectroscopy.
~=PI(CO)s
0
OEt
Fe
0
8.48
to form
paths.
retained
50%
[?21].
of dichlorobis(q-cgclopentadienyl)niobium
the carbynes (8.49; H = Cr, NO, .Acetylferrocene thiosemicarbazone
iron(11)
occurred
by different
250° but they
ferrocenyilithium gave the. ferrocengl-niobium derivatives (8.48; Treatment of the ferrocenyl gave
transitions
and air up to approximately
the
W;
with
complex (8.471 [122]. M = Cr, MO, W) with
X = Cl, Br, 1) [123]. has been treated with
complex (8.501 which was characterized In the same way l,l1-diacetylferrocene
0 0 0
Fe
0
8.49
G=M(co)4x
BX3
205
Fe
Fe
0 0
8.51
8.50
0 0
8.52
6 0
8.53
206 thiosemicarbazone
gave
The reaction c1*3. diferrocenylacetylene A similar
reaction
a polymeric
structure
gave
between
the mixed
carbon thr88
of the latter
of 1.462 A but
length
atoms
being Th8
atoms.
the eclipsed obtained with
salts
125
0.035
(8.53)
square
planar
and
determined
8.53). X-ray
average
with
with
by
one
of
bond
the
of
the
plane
rings
[125-J. cyclopalladated
formed
by
the
Of f8rrOCen8
ferrocene
other
were
in
(8.54) was
(N,N-dimethylamino)methylferrocene
(8.55)
active acids and sodium tetrachloroTypical acids used were N-acetyl-L-
acid
and lactic
acid.
in 70% yield
with
The cyclopalladated en enantiomeric
product
excess
of
[126-j, The
002K8,
ferrocene-palladium
COZ4e, COPh
CN,
Acetglferrocene to give the
enil
the complex
complexes
condensed
(a.591 which
with
combined
CuL2. H 2 0, where
/
with
complexes
2
Pd-
CH21DIe2
Cl
0
Fe
*
8.54
were
treated
S-methyldithiocarbazate copper
LH = the anil
of the ferrocenylphosphine
m8 \
8.56)
the corresponding
R1 = H, &i8, R2 = Ph 9 CO Et 2' R = COMe, COPh) [127].
and 8.58; was
(8.54 and
to give
ro- Q Reaction
0
was
was
quite
with olefins under mild conditions 1,2_disubstituted ferrocenes (8.57;
give
with
(8.51).
(8.52
the two isomers
ring
A out
active
obtained
wa-
complex
in methanol.
mandelic
(8.54)
chloride
0
of optically
palladate(II)
sandwich
y-cyclopentadienyl
by treating
valine,
gave isomer
was not
it
conformation
An optically
iron(I1)
dicarbonyl(y-cyclopentadi8nyl)cobalt
The ~ocyclobutadi8ne
anelysis.
with
of dicarbonyl(q-cgclopentadienyl)cobalt
and ferrocenylphenylacetylene Th8
complex
0 ‘3.55
(6.59) (8.60;
ions
to
c-1281. R' = ferrocenyl
/ QP
207
_
I
N
0
PdI
Fe
i
Cl
*
0 8.56
8.57
8.93
8.59
8.60 I
Q
COCH2AuPPh
0
CCCK2HgX
3
Fe
*
Fe
0
0
0
8.61
References
p. 238
,
I“
8.62
or phenyl,
R 2'-- Br) with
Grignard
reagents
gave
the corresponding
comporlnds ~(8.60; R' = Ph, R2 = Me; R' = ferrocenyl, & = D-Fc6Rq) R2 [i29]. organogold
The ferrocene-gold acetylferrocene complexes 8.
Chemistry
method
acylferrocene
with
of the alcohol
in
dilute
and gave
hydrochloric
acid,
without
isolation
the ferrocenylalkene.
For example, l-ferrocenyl-2-methylpropene in 92% yield
gave
this route
Cl34 The cis- and trans-isomers
been
complex
characterized
(8.64).
compounds
or
oxygen
and used
The reactivity
has been
reactions [132]. Treatment of Me)
of ferrocenylalkenes
This involved the reduction of an lithium aluminium hydride and direct treatment
with
isobutyrglferrocene
have
for the synthesis
was reported.
of the alcoholate
via
by treei5ng
.(Ph3PAu)3GfBF -. !?!heferrocene-mercury 4 X = Cl, Br, I) were also prepw8d [130].
(iv) General yield
(8.61) ‘PJasprepared
with
(8.62;
A general high
complex
studied
the tetrahydrofuran
suggested
formed
W< CR
of silica (8.68)
gel gave
whereby
in these and Grignard (8.65; R = H,
in hexane
and the butan-1,4-diol the dimers
ecN Fe
A mechanism were
3
0
8.64
with
the butadiene
dimerization.
0 8.63
Stefen
(8.66; R = H, Me)
by oxidative
for the reaction
Fe
the Pinner,
group
(I-hydroxy-I-a.rylethyl)ferrocenea
gas in the presence
(8.67),
of the nitrile
using
(I-arylvinyl)ferrocenes
derivatives
of the ferrocenylbutadiene (8.63) to form the iron tricarbonyl
produced
(8.69) was via
Fe
Fe
Ft3
Ff3
0 0
8.68
8.67
R
R
Fe
Fe
0 0
8169
Fe
Fi
*
0
0
0
8.70
210
fjypcH2c_cc~ccH20+=&? FE!
*
0
8.71
Fe
6.72
a six-membered molecular
cyclic
oxygen
Cgclizatlon with
hydrogen
basic
medium
The
of
the
addition
chloride product
underwent and was
sodium
hydrogen
chloride,
a typical
addition
aluminium a mixture
of
the
sdphide
water
reaction
were
cis-
and
and
of
the
as
a weakly
(8.72)
butgllithium
2-thienyl) when
the
trans-isomers
to
has
(8.73;
acetylene
chloride used
in
derivatives
ferrocenyl,
of hydrogen
chloride
incorporation
(8.71; R = Br, I)
thiOph8ne
(6.73; ii = Ph, In
by
[133].
molecules
corresponding
of hydrogen
investigated.
R = Ph)
olefin
ferrocenyl-acetylenes or
the
ferrocenylacetglenes been
two
sulphide gave
(8.70) formed
peroxide
into
acetyl
reagents.
The
of
olefin
the
211
i
Q 0
CEC-R
CCl=CHPh
0
Fe
Fe
0
a-73
a.74
(8.74) [135]. Th e cyclopropgl-substituted alcohols (6.75 ; R’ = R2 = R3 = Me; R’ = R2 = R3 = H; R' = H, R2 = R3 = Me; R' = R2 = H, R3 = Ph; R' = Me, R2 = H, R3 = Ph) were prepared from the corresponding ketones. (8.75; R' = R2 = R3 The alcohols = R2 = R, R3 = Ph) were converted to the methyl-ethers =H;R' (8.76;
R = H, Ph) respectively (8.75;
The alcohol corresponding
(6.77)
olefin
chromatography the other
R' = Ne,
on silica
the pyrazoline
derivative the presence
Similar
gel.
ferrocenyl-alcohols
The ferrocenylchalcone form
by methyl
listed (8.79)
(8-80;
ring
protons
in pgrfdine nitro-
in cyano-, containing
was
cyclized
were
gel.
studied
with
with
hydrazine
was acetglated thermal
and potassium (8.81)
trans-diferrocenylcyclopropane Hydrogen-deuterium
reactions
and underwent
carbon
of platinum,
and silica
[136].
R = H) which
(8.60; R = COMe)
alcohol
R2 = H, R3 = Ph) was converted to the and the ring opened product (8.78) by
to
to give
degradation
hydroxide
the in
to the
[137].
exchange
of the substituted
cyclopentadienyl
acetyl-
and benzogl-ferrocene
took place
10% deuterium
oxide.
Carboethoxy-,
formyl-,
and methyl-ferrocene
did not undergo exchange under these and l,l@-dibenzoyl-ferrocene l,l'-diacetyl-
However, conditions. underwent exchange in either pyridine or diglyme [I38]and The reactions of 1,2- and 1,3-diacetylferrocene diformylferrocene
with
aromatic
aldehydes
were
1,2-
investigated.
On
condensation with acetophenone the products from both 1,3-aacetYl_ ferrocen& and 1,2-diformylferrocene were stable but those of 1,2-diecetyiferrocene
Referencesp_ 238
(8.82
and 8.83)
underwent
decomposition
to
8.76
8.75
8.79
8.78
Q-p-Q Fe
*
8.77
Fe
Q-+9 Ft3
Fe
0 8.80
8.81
213
COMe z
Fe
0
COMe
0
8.84
0.02
COCH=CHPh COCH=CHPh COCH=CHPh
I.4
Fe
*
0 0
8.83
8.85
8.1
Scheme
give
derivatives
(Scheme The
8.1)
of 2-acgl-6-hydroxyfulvene
reaction
acglferrocenes
of Grignard
with
optically
with
thioglycoliic
(8.86).
in methanol aqueous
References
P_238
and 8.85)
thiols.
acid
was investigated
Thus
enantiomers
alcohols
[1401.
I-ferrocenylethanol
in the presence was
added
was treated
of trifluoroacetic
a salt which gave
liberated
on treatment optically
to optically
acid acid
active
ephedrine
(-)+-(1-ferrocenylethyl)-
with mercury(II)
active
with
by treatment
(r)-S-(I-ferrocenylethyl)thioglycollic
acid which
acetone
of acetglenic
resolved.into
intermediate
to form
thioglycollic in
were
active
to form
This
reagents
and acglcymantrenes
Ferrocenylalcohols
and acetone
(6.84
[139].
chloride
I-ferrocenylethanol
[lkl].
2x4
7HSCH2C02H
0
Ml3
Q.'
Fe
0 0
Ferrocenylboronic basa hydrolysis acid was
acid was prepared
of ferrocenglboron
converted
in good yield via the The ferrocenylboronic
dibromide.
into hydroxgfarrocene
and
this
was
treated
with
2,3-dihydroppan of this acetal Z-lithiated
to give the ferrocanylacetal (8.87)Lithiation (8.87) with n-butgllithium gave the corresponding ferrocane (8.881, which was used to prepare some
1,2-disubstituted
ferrocenes
("ferrocenyl-aspirin") The propargyl ferrocenrlcarboxylic
including
(8.89)
ester
(8,goj
was obtained
acid with
l,l'-ferrocenedicarboxJrlic
I-carboxg-2-aoetoferrocene
[l42]. proparggl
acid was
by esterification
alcohol,
obtained
the diester
in the
same wag
Co2H
0 13
QFe
Fe
Fe
00
0 0
0.87
of
[143]-
OCOMa
Li-0
0
of
0 0
8.88
8.89
215
C02CH2Cz
C02Me
CH
Fe
0
0
0
0
8.90
8.91
Acetglatlon acetic
COMe
of ferrocenecarboxylic
anhydride-boron
trifluoride
acid methyl
etherate
ester
or acetgl
with
chloride
gave
mainly the heteroannularly substituted derivative (8.91) but some I-carbomethoxy-2-acetylferrocene was also isolated [l/.&]. The ferrocenyl-esters (8.92; R = H, CO,PIe) were prepared by the electrolgsls
of ferrocene
and oxalic
acid
in methanol
on a
platinum electrode. Mono, bis- and tris-(3-methoxycarbonylpropyl)ferrocene were prepared by the electrolysis of ferrocene in the presence of ~Ie02C(CH2)3G02H [145]. The N-ferrocenylmethylpyridini-m to azidomethylferrocene water.
I *-Substituted
similar
reactions
Q
CO,Me
0
Fe
8.92
:
(8.94)
salt
on heating
ferrocenylethylazides
[l46].
t.8.93) was with
sodium
were
converted azide
obtained
in by
216
8.94
8.93
A number
of Schiff
ferrocenecarbaldehyde were
obtained
Typical
were
have
amino
and the compounds
products
DL-SRMe2,
bases
with
been
were
the carboxylic
L-CH2CH2CH2iDIC
by treating
Yields
in the range
used acids
DL-CH2CHIqe2, L-CR2CH2C02H,
L-CH2CH2SMe,
prepared
acids.
as haamatinic
r8.95;
DL-CH2C02H,
(=NH)HH2]
and their
The products
uuderwent
alkylation,
formylation
=
agents. H,
DL-Me,
L-E-CH~.C~H
ethyl
(8.96; R = H, Ph) were [(y-C5R5)Fe(y-CSHbCOCR2C02Et)]
. Ferrocenylpgrazolones ferrocenyldiketones
R
87-9556
esters
.oIi,
147 3. I!
formed from by condensation.
and coupling
with
reagents cl48 3. Formylferrocene was condensed with substituted hydrazines to (8.97; Y = IiH, NMe, NBz, NPh, 0, S) in yields of give hydrazones diazo
51-97s
[Q&9].
Q
CH=NECERCO;IH
0
8.95
8.96
217
f
CH2NHHe2
*
0 8.97
8.98
(Dimethylamino)methylferrocene salt
to form
the corresponding
substituted
was
treated
Reineckate
with
(6.98).
(dimethylamino)methylferrocene
the Reinecke
An
underwent
alkyl the same
reaction
[M]. The thermal
perchlorate subject
decomposition
of ferrocenylmethyldimethylammonium
and ethylenediferricinium
of kinetic
investigation
(Dimethylamino)methglferrocene in near
quantitative
yield
perchlorate
[IS+ was
oxidized
with hydrogen
have
been
the
to the N-oxide
peroxide
[152].
The
aminomethylation
of I,1 r-diethylferrocene and 2,2-bis(l,l'diethylferrocenyl)propane with his(dialkylamino)methanes [(R2R)2CH2 R = Irie,Et, Ru ]in
where
acid was investigated. bis(dimethylamino)methane
acetic
acid
in the presence
3-dimethylaminomethylferrocenes [153]. A series of ferrocenyl polyamines 8.101)
was prepared
diborane were
lymphocytic obtained
by reduction
in tetrahydrofuran.
subjected
to screening
leukemia
with
of phosphoric
With The reaction of l,l *-diethylferrocene gave a mixture of l,l'-diethyl-2and
P-388.
(8.99; m = 3, 4, 6.100
of the precursor
The polyamines for antitumor
(8.99,
8.100
activity
No significant
any of the polyamines
polyamides
and 8.101)
against
antitumor
or their
and with
activity
corresponding
was
pdg-
hyd_~obromides. However, the precursor polyamides [8.102: n = 3, R = H; n = 3, R = (CH2)2COI?H ; n = 2, R = (CH2)3CONR(CH2)2COIiH ] did exhibit
a low but
significant
(Dimethylamino)methylferrocene with
nucleophiles
References p_ 238
to give
antitumor
activity
methiodide
the corresponding
has
[I%].
been
treated
ferrocenylmethyl
218
Q
( CH2 ‘$JH ( CH2),m2
Q
(c~~)ql‘ra(CH~)~~~(~~2)3~2
0
0
Fe
F0
0 0
*
0 8.100
8.99
Fe
8.101
(cH,)~cONH(CH~)~COI~
_Q 0
8.?02
8.103
cH2NtixH2
219
-, Thus
compounds. hydrazine been
of nitrogen
prepared
the sodium product
in 80%
(6.103)
A number have
rezctiion
with
hydraAm
yield
ga7e
ferrccsnylmethyl-
[155].
heterocgcles
by treatment
with
ferrocenyl
substituents
of ferrocenylmethylchloride with A typical heterocyclic anion.
salt of the appropriate
was the ferrocenylmethylaminotetrazole
(8.104)
[I_%].
Fe
0 0
8.104
9.
BIFERROCERES, Ligand
FERROGEWOPRANES
exchange
(L = benzene,
reactions
mesitylene,
the dications
biferrocenyl
(9.2) were
-Q--Q 0
'Fe
9.1
Referencesp.238
L
and tetralin) were effected In the presence 'of one c'hloride. were
formed
isolated
and with
[157]. 2f
+
0
and arenes
naphthalene
in the presence of aluminium mole of arene the cations (9.1) arene
AND ANiK%_&IED FERROCERES
between
-@q-
Fe
Fe
Fe
L
L
L
9.2
two moles
of
220
Neuse
and co-workers
dilithioferrocene coupling
experiments
-taken to exclude
pure (9.3)
were used
formation
of cobalt
from
of I,I*-
chloride.
dioxide.
and the degree that step,
the coupled
of
of polymerization
the reaction followed
entity
were
A series
of di- or multi-nuclear
addition
In the
and precautions
and carbon
was obtained
from an oxidative
I
Fe
oxygen
the coupling
of cobalt(I1)
It was proposed
relatively high. via the intermediate
wes
elimination
studied
reagents
molecular
polyferrocenglenes
complexes
have
in the presence
proceeded cobalt
by the reductive
[ISS].
IT
Fe
Fe
9.3
Intermolecular in t'ne presence
coupling
'hydride and tributglam&e ferrocenyl)ethylene Catalytic
chloride,
mixture
to give
lithium
hydrogenation
of the unsaturated (9.6).
by the reductive
1,2-bis(l'-formyl(9.5)_
derivative
The ferrocenophane
coupling
occurred
aluminium
(9.4) and the [2,2]ferrocenophane
the [2,2]ferrocenophane prepared
of I,1 *-diformylfsrrocene
of a titanium(IV)
(9.5) gave
(9.6) >ras also
of 1,l *-di(hydroqmethyl)ferrocene
[?59]* T%e synthesis and
of [Z]orthocyclo[2](?,2)ferrocenophane
[2,2](1,2)ferrocenophane
trimethylammonium phosphorane and then
salt
(9.11) has
been
(9.7; X = N+Ke31-)
(9.7; X = PiPh31-)
to the
to the diferrocenylethane
was
(9.10)
reported.
The
converted
via
diferrocenylethylene
(9.9).
Cyclization
the (9.8)
and
subsequent reduction gave the ferrocenophane (9.11) as a mixture T'ne orthocycloof two isomers (9.11a and 9,llb) in the ratio 3:l. ferrocenophane stereochemistry
(9.10) was
synthesised
of toe lerrocenophanes
by a similar
route-
(9.10 and 9.11)
was
The
221
QcH=cHQ OHC
CHO
@CH=CH.@)
9.5
9.4
Fe
Fe
@cH2cH2--@ 9.6
compared chair,
with
boat
of [2,2]orthocgclophane
and twist-boat
conformations chair
that
conformations.
for the trans-ferrocenophane
(q.731,
(9.~6).
exo-erdo (9.141, -endo-exo -it was considered that the most
(9.12) wnich
may
adopt
The four possible (9.'l?a) are -exo-exo boat (9.15) and -endo-endo favourable
conformer
was
Similar arguments were developed the -exo-exo chair.form (9.13). for the cis-ferrocenophane (9.11b) and for the orthocgcloferrocenophane
(9.10) [160]. The synthesis of some trimetii~lene bridged ferrocenes has Previous reports that the tribridged compound reinvestigated. (9-17) could were
References
shopm
p_ 233
be converted
to be incorrect
to the tetrabridged and
the last
ferrocene
compound
(9J8)
been
(9.16) has
been
Fe
Fe
Fe
:@
6 0
0 9.8
9.7
9.10
9.9
9.11a
- fzmns
9.11b
-
cis
223
x
exo-endo
- 9.14
I
11
_I A--kFeA endo-exo
6X0-8X0 rsfomulated to prepare obtained
endo-endo
- 9.13 as the
homoannular
a'pent=bridged
bridged
ferrocene
potentials
for ferrocenes groups
The conformations
showed
bridged
and configurations
(9.19).
- 9.16
Attempts
the product
bridges.
with
a correlation
ferrocene
were unsuccessful.,
(9.20) -contained homoannular
methylene
- 9.15
one, with
The electrode two and three tri-
the engle
of several
of ring-tilt.
bridged
ferrocenes
were
discussed and related to previously reported Noessbauer results structures of three multibrieed [161]_ Th e crystal end molecular
ferrocenes
(9.19, 9.20 .znd 9.21) hsve been co_nfirmed by X-rag One of t'nese structures (9.19) had been claimed crystallography. previously by kchl~gl and Peterlik [162)as the tetrabridged ferrocene
Refer&es
p. 238
(9.18)
[163,
164,
1651.
224
9.17
9.19
9.21
9.18
9-20
225 1 H and.13 C MR structure
and coupling and were The
spectroscopy
have-been
[3] ferrocenophanes
of the
constants
in agreement
for with
the bridge
in borax
approximately Photo-oxidation (9.26) and
240
occurred
acids
(9.24) and
in the presence
to give
(9.25) were
with
light
of nitrous
the corresponding
9.24
I
Refere.ncesp.238
9-26
of oxide.
zwitterions
(CH213C02H
9.25
[166].
structures
[167].
9.23
the shifts
were obtained
atoms
proposed
of pH 9 arid irradiated
run wavelength
(9.27)
9.22
buffer
investigate ChemLcal
9.23).
hytiogen
the previously
4-([3]ferrocenophanyIngl)butanoic
dissolved
used.to
.(9.22 and
9-27
226 The
dihgdrodicgclopentanaphthalene
the corresponding binuclear last
converted
to
and then to the The binuclear chloride.
ferrocene (9.30
c5?3 00
\
(9.28) was
with n-butyllithium
(9.29) with iron In the and 9.31) were formed in the same way. proportion of the trinuclek ferrocene (9.32) case a small [168]. obtained from the trianion and iron(I1) chloride
ferrocenes was
dianion
/
Fe
Fe
Fe
0 @ 9.29
9.31
00° 9.30
Fe
Fe
0
9.32
227
n
10.
FERROCENE-CONTAINING The preparation
has been
discussed
POLYN3RS
of ferrocene by-Korshak
l,l'-ferrocenedicarboxylic
monomers
and their
and Sosinb@].
polymerization
Ethylene
acid-terephthalic
glycol-
acid copolymer
gave
fibres with good photostability and oxidative thermostability. The crystallinity of these fibres on orientational elongation and the degree
higher
of orientation
dimethyl
ferrocene, modified
terephthalate
polg(ethylene
was
lower
than
fibres [170]. and polgcondensation
polg(ethylene terephthalate) me transesterification
and ethylene
terephthalate)
that
was
of
of I,l'-diacetyl-
glgcol
containing
gave
a
l,l*-diacetyl-
The reaction involved the intermediate formation ferrocene groups. of dioxolane derivatives of the substituted ferrocene and the subsequent formed
cleavage
fibres
light
of these
which
and under
poly'(ethylsne
showed
oxidative
Fibre-forming of dimethyl proportion
C
compositions
or break
when
isoprene,
obtained glgcol
with
by the copolymerization
together
did not
elongation
and
terephthalate),
suffer
after
with
a small
or l,lt-dibutyrglferrocene.
the poly(ethylene
UV irradiation
chemically
1-12s
Fibres
a reduction
was homopolymerized
butadiene or
Various
and
obtained
in mechanical for ten days at
in the presence accompanied
containing
polymers
chloride)
of aluminium
chloride.
were
in
the
obtained
treated
Soluble
composition
unsaturated the Vicat
of
the
polyesters softening
Referen-p.233
of
was also
with
polymers
reactions,
ferrocene containing substitution
[174].
A fire-resistant unsaturated resin has been 1,2-polybutadiene with ferrocene in the presence Good fire resistance with an amine hardener
presence
such aschlorinated
were
and in most
by dehydrohalogenation
[175].
with
[173].
metal
and polg(viny1
up to 62% ferrocene
and copolymerized
l,&dibromohexane
lithium
halogen
polyethylenes
me
by
[l-72].
n-butyllithium
resin
compared
the transesterlfication
copolymer
Vinylferrocene
was
were
ethylene
catalyzed
into
the brown
strength
conditions
polymer
to degradation
['l71].
terephthalate,
incorporated
40°
stability
of 1,l I-diacetylferrocene
The metallocene from
thermal
terephthalate)
The modified
intermediates.
improved
formed by heating of benzoyl peroxide
by curing an epoxy in the presence of ferrocene [I76-j. oligoester used to form ferrocene-containing
has been
point,
shown
the Brine11
achieved
theoretically hardness
to determine
and the Stress
228
Causing
failure
shotred high They
were
during
bending
reactivity
proposed
of the polyesters.
were
and
as binders
amenable
to hot
for glass
of vinylferrocene composition
was
with
was based
vinylferrocene
obtained
suitable and AIBN
2 parts
or 1,2-polg-
A typical
50 parts, which
plastics
copolymerization
monomers.
on 1,2-polybutadiene
30 parts
polyester
by the radical
organic
polymers
fibre-reinforced
and electrical insulators [177]. A fire- and heat-resistant unsaturated 'outadiene composition
These
or cold curing.
stgrene
were
heated
five hours
at 100° C to form the cured resin, The resin for 250 hours at 15Oo C without any change in electrical mechanical properties and without the evolution of smoke
50 parts,
for
was heated and OF
t0X.h
f’umes
[178]. Ferrocenylacetglene of THF' and ethanol using
has been polymerized at 60° C in a mixture bis(triphenylphosphie)nickel(II) halide
The polymer was separated by precipitation complexes as catalyst. cm-l with ether and had an electrical conductivity of IO -IQ-1 [179]. Polg(acrgloylferrocene) fractions
and the thermal
temperature
at which
was measured eratures values
was
divided
stability
10% weight
loss
for each fraction.
The
of 310° C and
of 250°
350° C while
into
soluble
of each was
investigated. The in air and in helium
occurred soluble
fraction
the insoluble
C and 320° C respectively.
The
thd stability
of poly(methy1
acryloylferrocene
Acryloylferrocene methacrglate
was
and styrene
as the initiator,
methacrglate) [1803. copolymerized
in benzene
The last
using
thermal
two copolymers
was with
gave
fraction
of polystyrene, poly(acrylonitrile) and poly(viny1 enhanced by the incorporation of acryloylferrocene incorporating
and insoluble
stability
acetate) residues
decreased vinyl
tempgave was but
by
acetate,
methyl
azo-bis-isobutyronitrile were
obtained
in 80%
yield or better and while some homopolymerization of the organic monomers was detected, acryloylferrocene did not form a homopolymer under these conditions. 'The ratios of acryloylferrocene units to organic
units
were
1, 0.59
and 1.37
for vinyl
acetate,
methyl
methacrglate and styrene respectively [I~I]. Ferrocenylmethyl methacrylate underwent anionic polymerization in a high vacuum system using lithium aluminium hydride-tetramethylTne living polymers obtained combined ethylenediamine as catalyst. with
methyl
methacrglate
"rile and acrylonlti
to give ferrocenglmethyl
229
methacrylate-methyl
methacrglate
acrylonitrile
copolymers
of
SkgreEe
since
block
to
the living
the polymerization methyl
polymer
anions
the polyxner
were
to living
Interfacial ferrocene
was
obtained
copolymer by adding
[182]. has been used
condensation
a block
the addition copolymer
as nucleophiles
The block
polystyrene
methacrylate-
However,
dfd not give
too weak
of stgrene.
methacrylate-styrene
monomer
and ferrocenylmethyl respectively,
to initiate
ferrocenylthe ferrocenyl
to prepare
dioxime-di(T-cyclopentadLenyl)titani.um
l,l'-diacetyl-
dichloride
The importance of stirring copolymer in near o_uantitative yield. time, stirring rate, monomer ratio and solvent on the reaction was
evaluated
['l83].
Vinylferrocene with
radical
azo-bis-isobutyronitrile
ization with
underwent
was linear
ti-me-
tow20$
Aggregation
precipitate
ccnversion The ZSR
snd then
of paramagnetic
species
poly(g-vinylbenzophenone) occurred chain
light.
and recombination
resulted
in intra-
of the ferrocene
group
irradiated
with
increases break
and decreases
was dependent dose
increasing
and then
were
decreases
the quantum
with
ferrocene
doses
of x-rays
in tensile
in solubility,
on the proportions
irradiated
located
and inter-molecular
chemical reactions [ISS]. Copolymers of ethylene
a
confirmed
and
copolymer
of the benzoquinone
of t‘ne radicals
reduced
caused
of the polymer
block
in iso-propsnol
Photoreduction
progressively
conversion
[184].
p-Vinylbenzophenone-vinylferrocene ultraviolet
of polymer-
decreased
at high
spectra
in benzene
The rate
as initiator.
of the polymer
to be formed.
the presence
polymerization
The
in the polymer The presence
reactions. yields
with
groups
,
in the photo-
a.2d v?.nylferrocene were and showed sequential
strength
a-n-delongation
detailed
form
of comonomers
and
at
of the changes
the radiation
[136]. The
thermochemical
copolymers
with
polg(ferrocenylmethy1 styrene
of polyvinylferrocene,
its
and methyl
methyl acrylate and methyl methacrylate; methacrylate) and its block copolymers with
methacrylate
were measured
over
the temperature
thermogravimetry and an automated Polyvinylferrocsne was found to undergo torsional braid technique. irreversible changes in the temperature range 220° to 3oo" so that
range
-180~
properties
styrene,
to 250° using
the glass transition temperature (Tg) was not obtainable directly ^_ but extrapolated from the Tg values of its random copolymers-
References p. 238
230 a low value
was
obtained
by this method
value of Tg for poly(ferrocenylmethy1 that obtained by direct determination. by m-bis&-PhenoxyphenoxyIbenzene concentrations polystyrene
with
of plasticizer
Polgferrocene method
several
film
films
have been
th$9snesses
11.
was plasticized
in Tg at low
than
in plasticized
by the plasma
small
Results
arose
of plasma-polymerized
from
for
the
ferrocene
constant
investigated. for aluminium-polyferrocene-aluminium tans, showed
polymer-
measured.
that conduction
The dielectric
increases
E
and the sandwich
in the temperature
range
[189-j.
APPLICATIONS
OF FRRROCETJE
(i) Ferrocene
catalysts
The incorporation density
gave
use when
quality
into
low
a photodegradable
formed
the soil temperature
and nutritional
and photosensitizers
of 0.0_5$ oc-hydroxyethylferrocene
polyethylene
agricultural crops
polymer
to
[I883.
current
.tb.in-films were
30-400’
formed
conduction
suggested
Tfiedielectric properties factor
This
was equal
a decrease
that was greater
and the electrical
space-charge-limited
structures,
the extrapolated
[187],
ization
loss
but
metbacrylate)
into
was
material suitable for When used on potato thin film.
increased
of the crop
by 2.5O
improved
C and the yield
[?90].
The photodegradation of polyethylene was accelerated by the introduction of a small proportion of acetoxgferrocene or d-hgdroxgethylferrocene,2,4-dinitrosoresorcinol into
the polymer
[191].
Photodegradation up to three-fold were
added
of coloured
when
of patents
groups
on polymers
was
together
with
having
O,Ol-20
was
enhanced
and iron(ii1)
by oxide
b92]. taken
deriva-tives in positive-warking were based
polyethylene
1-hydroxyethylferrocene
as photosensitizers
A series
and benzophenone
out on the use
radiation
of ferrocene
The resists
resists.
halocarbonyl
and/or
wt f of a ferrocene
carboxylic derivative
acid [ll.l:
R' = R2 = OH, CH20H, (CH2)20H, (CH2)30H, (CH2)40H]as a sensitizer Similarly a series of other ferrocene derivatives were [7931. The addition of the used as sensitizers in a range of polpers. ferrofene
derivatives
of the resists
greatly
increased
[?94, 195, 196, 1971.
the electron
beam
sensitivity
231
Q
R'
0
Fe
0
0
R2
11.1
Radiation
resist
compositions
were
prepared
that
contained
O-1-30 Wt $ of a metallocene (11.1; R1 = R2 = R, OR, ~_hy&oxyalkyl, CHO, C02H, alkoxgcar"oonyl, halogen; K = Fe, Ni, co, cr, r~l, RU). The resists integrated
were
circuits
A light from
that
useful
composition
or a ferrocene
and an analytical
with
reagent
image was
this wasfixed
an image
composition
derivative for
iron
an organic
obtained
2 parts
and polystyrene and acetone.
on exposure Thus, iodoform
and gave
a clear
blue
10 parts
were
The solution image
after
colour
by mixing halogen
by mking
dye, ferrocene
compound
was
4.2
dissolved coated
exposure
iodoform,
and a binder.
of the composition 4 parts, 3,3-bis-
(dimethylaminophenyl)_6-dimethglammophthalide toluene
in
[199].
obtained
by heating.
different
was prepsred
wFth
compositions were Photoimaging the leuco form of an 2cid sensitive A coloured
and
[198].
sensitive
of the unmodified
ferrocene
of semiconductors
for the fabrication
parts,
and
ferrocene
in a mixture
of
on a polyester
and
fixing
base
[200].
Phototiaglng For example,
compositions containing ferrocene were prepared. 3,3-bis-(L+'-dimethylaminophenyl)-6ferrocene, trichloroacetamide
dimethylaminophthalide, dissolved
in a mLxture
polyester
film
References
which
p. 238
me
support.
_at 110~ to give clear Ferrocene formed bromide
of toluene
was
film
and polystyrene
blue images (2011. a charge-transfer complex
active
were
and acetone and coated on a was imagewise exposed and fixed
photochemkally
with
and was used
carbon
tetra-
to form
232 photographic was
images.
implicated
The formation
in the production
A photosensitive anodized
aluminium
composition
foil with
of ferricinium
of images
was prepsred
a mixture
tetrabromoferrate
[202]. by whirl
of a halogen
coating
an
containing
and a plasticizer in dic‘nloropolymer, carboxymethylthioferrocene The plate was exposed imagewise and then developed with ethane. a solution of Teepol in aqueous ethanolic sodium hydroxide to give a plate
'with improved
ink receptivity
Dimethylterephthalate in the presence
and ethylene
photoinduced
suspension
tetrachloride
as the initiator the water
were
ion was
the ferricinium
ion to ferrocene
of polymerization the addition
rate.
It was of the
n-Type a cell
layer
silicon
together
irradiation
of sodium
in the lauryl
of polymerization bromide
was
decreased
affected
as a stable
to electricity.
in less
than
(ii) Ferrocene The use
was
oxidized
approximately
silicon was
The
the
ion
by the
photoanode
in
other
of ferrocene
and fillers.
100s
ion at a
efficiency.
Prolonged cell gave a constant
of the ferrocene-ferriciniu which
It
dropped
by more
couple than
90%
[206-j.
stabilizers
it was
couple.
to the ferricinium
in a one-compartment
obtained
ten minutes
investigated
when
the ferricinium-ferrocene
In the absence
Photocurrent
binders
with
with
of the
a lower
catalyst
of light
that
of ihe ferricinium
layer
[205]. sho1.m to behave
t'nat ferrocene
photoanode
was
the transfer
to the water
was
an increase
The addition the rate
showed
acid reduced
in the cell were a platinum cathode and an electrolyte of au ethanol solution of tetra(n-butyl)ammonium
photocurrent.
againg
that
emulsifier
silicon
perchlorate was found
was
of
arid carbon
In the suspension which
of ascorbic
and there
increased
for the conversion
components consisting
Addition
blue
of cetgltrimethylsmmonium
suggested
the monomer
became
of the FWL.
as an emulsifier
whilst
charge
formed.
polymerizations
of ferrocene
investigated.
layer
the ferricinium
from
and emulsion
(NiW) in the presence
photopolymerization
sulphate
were POlyIWPiZad
to give poly(ethylene
[2O4].
methylmethacrylate
rate
glycol
of ?,I'-diacetglferrocene
terephthaiate) The
[203].
and improvers derivatives as inhibitors of Polyethylene Ferrocene behaved as a dehydrogenation
[207].
added These
to friction materials
materials were used
containing
organic
in the formulation
of raiI=Y prevent
brde
shoes and the presence fade [208].
brske
k storage-stable on cadmium benzogl
surfaces
peroxide
been used
has
anaerobic
composition
was prepared
and ferrocene
from
(11.3)
The 2-ferrocenylbenzoquinoine and polyamide
helped
capable
to
of hardening
oligocarbonate
[209].
acrglates,
The diacetglferrocene
as a dye for polyjethylene
for polyester
Q 0
of ferrocene
terephthslate)
has
materials
been
(11.2)
r2101.
claimed
as a dye
[211].
COMe
0
Fe
0
CONe Fe
*
0
11.2
11.3
(iii) Ferrocene Ferrocene amperometric slags.
in analysis in ethanol
titration
acid was added
The kinetics and vanadium(IV) that
of vanadium
could
by ferrocene
acid and acetic could
titration with Solomatin mination Iron(III),
acid.
be determined
was It was
media
The found
in steels
out
that
with
and rhenium(VII!
determination titration
vanadium(V)
alloys
were
of
of sulphuric and vanadium(IV)
by amperometric
a method using
[212).
investigated
in a mixture
devised
case and
vanadium(V)
were
of each other
and
in metallurgical
of vanadium
amperometric
carried
the
in each
for the titrimetric
ferrocene [213]. and co-workers have
molybdenum(VI)
Reference.sp.238
of ferrocene
in the presence
of molybdenum
was used
aqueous-organic
be selected.
for
and iron(II1)
in the determination
cond9tions
vanadium(V)
as a reagent
acid medium
of the reactions in acid
the opt5m~~11
used
of vanadium(IV)
An acetic-sulphuric
phosphoric
SO
has been
for
the deter-
ferrocene
determined
[274 ]-
inairec*lY
by reaction
with
ferrocene
to give
the ferricinium
ion
and the concentration of this latter ion was estimated spectrophotometrically at 675 nm. Molybdenum(VI) and copper(II1 behaved as interfering ions in this estimation whilst manganese(II), iron(X), metals
cobalt,
did not
nickel,
interfere
The amperometric ferroeene
in acetic
The best
medium
for
Under
leadfIr), but
these
nitrate
zinc(II),
of the conditions by ferrocene
The optimum
conditions
mixture.
interfere
but
chrom;-Um(VI)
iron(III),
with
investigation.
A ferrocene
6M hydrochloric acetic redox
acid.
dimethyl acid
couples
A series cyanide
been
was
cations
of ferrocenes
of Cu2+/Cu+ electrodes.
tetrafluoroborate The properties
found
and immersed
silylferrocene Cyclic
voltmetrg
electrolyte
was
difference
germanium
in an iso-octane
lOrg
aqueous
of hydrochloric Se/20 mL any
[218]. by coulometric
reaox were
and the
acid,
system
oxidized
titration,
in methyl
of 20-50 mV between
The ferrocenes
with
and the ferricinlum/ acetic
was
was determined
[2.19], of n-type
(11.4)
limit
as an auxiliary
order
at a range
examined
was used
in SO,% aqueous
to be second
in aqueous
of
of a kinetic
of 0.025M
propanol
surface-bound ferrocene residues germanium crystal was pretreated acid
acid-
and
titration
the subject
concentration
The detection
ana a potential
indicator
mercury
for the emperometric
have
and aqueous
by metal
acetic
did not
[217].
determined
were
concentrations.
by the use
in a 1 :I
silver,
ion
did
solutions.
metals
of the selenium(N)/selenium(O)
sulphoxide
interference
acid
and alkali
acid as the supporting The reaction
potentials
ferrocene
earth
tsllurium(IV),
for the amperometric
in aqueous-organic
~3% sulphuric
necessary ferrocene
acid containing
ion and phosphate
required
with
investigated-
and silver(I)
thallium(III),
did interfere
The conditions selenium(IV)
were
The alkaline
was
thallium(I),
iron
copper(
titration water
earth
and mercury(II)
P acetic $5'0"
was
conditions
interfere [216). A st;udy was made of lead(IV)
and alkaline
acid mixtures
the titrations
selenium(IV),
interfere
of mercury(I)
acid-perchloric
acid.
alkali
zinc,
[215].
titration
3N perchloric did not
caomium,
platinum
by copper
sexniconducCors
with
have been investigated. The by anodization in 6~ sulphuric solution
of either
tricfiloro-
or I,1 '-bis(dichlorosilyl)ferrocene
of the derivatized
surface
in ethanol
(11.5). or
235
0
Q
SiG13
0
Si(OEt)3
0
Fe
Fe
is 0
0
?1.4
11.5
acetonitrile
11.6
of tetrebutyk3mmonium
SohtiOns
si(ost)j
0
perchlorate
confirmed
that the r'errocene groups were firmly bound to the surikce. the electrode caused the anodic current peak to Ilhminztion of be moved by up to -200 mV to more negative values Mhich was consistent with the anticipated photoeffects for an n-tgoe semiconductor, Comparisons between the derivatized electrode and a naked n-type germanium photoelectrode in electrolytes containing ferrocene indicated that the interface energetics and kinetics prere unaffected by derivatisation [220]. Platinum and gold electrode surfaces have also been derivatized with the silglferrocenes (17,k, 11.5 and 11.6). The ferrocene groups appeared to be bound to the metal by Si--G+I linkages where $1 = Pt, Au. me derivatized electrodes gave persfsteni; cyclic voltanznetric ferrocene
one-electron surface
was
Several acfd,
waves
at a potential
expected
derivative anu the parameters system. founu
Greater
in each
case
ferrocenecarboxylic
I,?'-ferrocenedicarboxylic
(71.7 and 11.8) r-leretimobilized
for an electroactive
accorded
than monolayer
with
coverage
a reversible, of the
[2273, acids acFu on
including
ferrocenylcarboxylic
and the carboxylic
a plat;lnum oxide
acids
electrode
residue. !Fhemode of binding is idealized for fesrocenglcarboxylic acid in the Iu;lide(11.9). X-ray photoelectron spectra were obtained and were used to support the structural assignments of the bound metal3_ocenes. Cyclic vo3.tammetry was used to investigate the electrochemical properties of the modified electrodes and the surface
tbrougb
Referencesp.2383
a 3-(2-eminoethylzmino)propgltPimetho~s~l~e
236
Fe
Fe
11.7
Q
11.8
*
~oEH(~H~)~~(CH~)~S~-O~
0
2 :
11.9
second-order case
of
ferricinium
ferrocenglcarboxylic
Darameters
were
immobilized
(iv)
Combustion
the added
pollutants,
to
acid
and
i:er& described.
tine non-ideal
ferricinium
over
with
monolayers
protection
The treatment
mineral
product
in
surface
stability
the
activity
was
enDanced
for
[222].
against of
ferrocenes,
oils,
non-basic
of polgethanolamine
It gave
gasoline.
substituted
kinetics
control mixed
car_densation
and was
and
smaller
multilayers
Perrocene
[223].
decay
coal
a reduction corrosion
with
and
iron
hydrogen,
and
in
and
ester
the
fatty
emission
carburettor
compounds, nitrogen
solvents of
cleansing
such or
acids
as
carbon
ferrocene
237 monoxide such
at
250°
increased
as
pyrites,
and
methods. _ -
Clean
coal
(v)
Biochemical
the
urine
and
B
and
Rats were from
oral
(approximately
only
sulphate
shown
of
in
of
the
small
in
its
The
prepwed was
absence
md
tfielr.
in
of
impurities
by
magnetic
this
method
(UDPGA)
(11.10)
was
A
which
the
Metabolite
in
A,
thought B was
metabolism
was
related
a
shown
to
ferrocene and
in vitro
to
the
observed
if
incubations
[225].
compounds
in mice
to be
cofactor
formed
added
not
activity
of
NADPH
was
was and
and
dose)
ticrosomes,
glucuronide
antineoplastic
oil
metabolites
metabolite the
In vitro,
sesame
isolated.
end
hydroxyferrocene
ferrocenyl-amide
by
Two
quantities,
uridine-St-diphosphoglucuronate but,
ferrocene
were
liver
Ferrocengl
oxygen.
yield
administered
intact
viable
separated
98%
collected.
of hydroxyferrocene
require
to be in
was
glucuronide.
to
moleculer
26%
susceptibility
applications
doses
remained
present
ester
ferrocenyl
was
biological
animals
which
these
obtained
these
nucleus
be
enabled was
given
ferrocene was
t&magnetic
Were
against
sarcoma
[226].
studied
Fe
0 0
11.10
A number synergists the
for
deposit
ferrocene to
Musca
ineffective
of
kn9"
left and
substituted
ferrocenes
insecticides
after
and
evaporating
were
shown
of
[ZZ?].
whereas
the
components
as
example,
1% c(-propionyl-
2-isopropyloxyphenyl-N-methylcarbonate
domestica
behave
For
acaricides.
a mixture
to
themselves
was were
lethal
238
Ferrocenylcholine were
shown
to inhibit
the enzyme
horse
Ferrocene agricultural acetic
acid
serum
derivatives
2
Aced, Sci., 295 N. s. Kochetkova
9
after
as iron-containing
dilution
and mixing
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was used
W. J. Pannekoek
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claimed
Ferrocene was treated with trimethylacid at 100° C to form trimethylacetgl-
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Ispgt.
(1978) Abstr,
Xo.
20G251;
215
47895. V. T. Solomatin,
276
Iihim.. 32 (19771 302. V. G. _yLochkova, V, T. Solomatin, Ignativ,
Izv.
Uchebn,
Chem.
Abstr.,
90 (1979)
and S. P, Rzhavichev,
G. V. Kozina
Vyssh.
and L. A.
(1978) 30; From Ref.
S..P.
Zaved.,
Rzhavichev
Khim.
Zh. Anal. and V. I.
Khim. Tekhnol.,
20 (1977) 677. 217
Rlochhnya, Izv, 20
218
V. A. Balusov, S. P. Rzhavichev
V. T. Solomatin,
Vyssh,
Zaved-, Khim. W-
Uchebn,
and V. G. Tekkrlol-,
(1977) 1472.
219
Zavod. Lab., V. T. Solomatin, V, A. Balusov and G. V. Kozina, & (1978) 1060. H. L. Kies and B. Ligtenberg, Fresenius' 2. Anal. &em,, 287
220
J. M. Bolts
221
M,
(1977)
142.
Chem. Sot,, 100 (1978)
and 15. S. itrighton, 5. Amer.
5257. S. Wrighton,
A. B. Fischer
M,
C.
Palazzotto,
and
L.
Nadjo,
and
R.
U. Murray,
A.
J. Amer.
B.
BoCarSLY,
Chem.
Sot.,
J. I& Bolts, 700
(1978)
7264. 222
J. R.
Lenhard
223
(1978) 7870. M. Lachat (Auto1 A,-G.),
Chem. Abstr., 224
J. X,
225
R,
Kindig
89 and
(7978) R.
L.
Swiss
J. Amer.
Pat.
Chem.
599464,
SOC.,
1978 r=Y
100
31;
132252. Turner
(Hazen
Research) US Pat. 4098%4,
1978 Jul. 4; Chem. Abstr., 89 (I?781 217845. p. Hanzlik and ';J.H. Soine, J. Amer. Chem. sot-, 100 (1978)
1290.
250 226
G, N. Ysshchenko,
227
Khim.-Farm, zh.. 12 (1978) 68. v. Hues and U. aBhrenz, '(Bayer A.-G.)
228
w. H. Kim,
Gorelova,
1978 229
Sep.
89
21; Chem. Diss,
(Bayer), (1978)
Abstr..
Abstr.
90
Ger.
Pat.
L. A.
and L. B. Radina, :
Ger.
(1979)
Int. B, 39
196207.
G. &I. Anoshtia,
L. V. ALekseeva
N. G. Evstfgneeva,
J. Niggemann Abstr.,
A. A. Shashmuriria,
(1978)
2702628,
Pat.
2711546,
1705. 1774. 1978
Jx.11.27; Chem.
ANNUAL
SURVEY
GEORGE
EARR
Department
COVERING
THE YEAR
and BERNARD of Physical
Wolverhampton,
WV1
1978+.
W. ROCKETT Sciences,
ILY
(Great
The
Polytechnic
Britain)
CONTENTS 1.
Revieus
2.
Structural
3.
Stereochemistry
4.
Spectroscopic
5.
Reactions
6.
Ferricinium
163 164
determinations of ferrocenes
166
and physico-chemical.
studies
170 175
of ferrocene salts
180
carbenium 7.' Ferrocenyl Ferrocene chemistry 8.
ions
186 160
(i) Photochemistry (ii) Derivatives (iii) Complexes (iv) General 9. 10.
Biferrocenes,
11.
Applications
metals
(metalloids)
202 208
ligands
chemistry ferrocenophanes
Ferrocene-containing
and annelated
219
ferrocenes
227 230
polymer-s
of ferrocenes catalysts
(ii) Ferrocsne
stabilizers in analysis
(v) Biochemical
230
and photosensitizers
(iii) Ferrocere (iv) Combustion
1.
other
of ferrocene-containing
(i) Ferrocene
12,
containing
190 193
232
and improvers
233 236 237
control and biological
applications
238
References REVIEXS Sutherland
and co-workers
have
presented
a review
hydrogenation of aromatic ligands during exchange ferrocene and arenes in the presence of alumkum .mechsnism
of the.hydrogenation
applications.
were
considered
*Ferrocene, AMual metal. Chem., 167
Surve (1979
was
discussed
on the
reactions chloride.
between The
and the synthetic
.[I]-
covering iAL year 1977 see J. Orgznop. 53-I-54.
164 The applications
of
(T-cyclopentadienyl)transition
complexes Solomatin
have been discussed by Kochetkova has revieued the use of ferrocene
chemistry
[3].
of the 1976
Ferrocene
literature
The chemistry
[41-
in a wider
review
STRUCTURAL
2.
Tne
have
been
mixed
each
the application out for
complexes
ligands
a good
linear
the charge density evidence indicated character X-ray
rings
structure
density
from
analysis. from
carried were
ring
proton
out..
found
in
proton,
on the free
level 2g levels having
was
ligand,
change
in
and there ionization
_ The crystal
groups
the y-cyclopentadienyl
(71.
studied
degree
by ultralong-
of delocalization
was an appreciable energies
and molecular
and decamethylferrocene
In both molecules The methyl
formation
was a high
for the e
50 kJ mol -' [S-J.
staggered.
Calculations
also
the corresponding
of ferrocene There
of sgm-octamethylferrocene
deviated
were
for a given
on complex
approximately
uere
such as ferrocene,
on that proton. It was concluded that the an appreciable diminution in the aromatic
in energy
X-ray
with
(T-hydrocarbon)
formation
the appropriate
correlation
approach
complexes.
snd C7H7+ shift
were
orbital
metallocenes,
on complex
3d population
by
included
SCF x0 calculations
diemagnetic
C6H6
order
spectroscopy.
of electron
INDC
and half-sandwich
for
of the ligand
The electron wave
[6].
including
The 'H ?7PiRchemical
to the shift
compounds
of the molecular
several
CsH5-,
in then--bond
case.
complexes
has been
[s].
and related
considered
complexes
sandwich
showed
was
metal
Reductions
in a review
and 7-arene
ferrocenes
and Kowarsch
of ferrocene
carried
for the free
relative
of q-cgclopentadienyl
by Volz
compounds
transition
included
DZTE~~IINATIONS
and
to these
has been
of heterocyclic
structures
discussed
chemistry
metal
and Krynkina [Z]. compounds in analytical
were
the
structures determined
-cyclopentadienyl ? in z-octemethylferrocene ring plane
being
of
rings
inclined
away
the iron atom.
determination temperature The
High thermal motion prevented an accurate of the geometry of decamethylferrocene at room
[9].
structure
of 2-silver(dimethyleminomethyl)ferrocene
(2.1)
The silver atoms formed a was investigated by X-ray analysis. planar square with the substituted ?-cyclopentadienyl rings acting as bridging ligands through one of the carbon atoms Of each ring. The nitrogen
atoms
did not
appear
to participate
in a distinct
165
Fe
2.1
2.2
coordination (2,1) were
of the silver also
atoms.
investigated.
of the Complex
Some reactions
Thermal
(2.1) and cymantrenylsilver
cp~trenyl derivative (2.2) and symmetrical-radicals PCIThe crystal
and molecular
of the complex
decomposition gave
the coupling
structure
of a mixture
the ferrocenyl-
products
of
of ferricinium
tetra-
chloroferrate was determined by X-ray diffraction. The q-cgclopentadienyl rings were almost eclipsed and nearly parallel. The inter-ring
distance
of ferrocene. does not
X-ray
chanels
x which
concluded
diffraction on cooling consisted
of channels enclosed
study
bond
of three
density
were
The crystal (2~5~ K) phases
structures in ferrocene
[II]. to a single-
with
7 and 32.
rings
were
delocalised
of the ordered determined
were
temperature
formed
a
of 120°. Within
occupied
the iron atoms were
which
a pitch
32 were
in
transition
At the higher
molecules
syrmnetries 3,
around
of an electron
subjected
phase
to 100' K.
of thiourea
d?mensionally
observed
was
to that
at 29s" K and the changes
channels, sites of point symmetry iron atoms. The ?-cgclopentadienyl regions
distance
a reversible
dotm
identical
the removal
clathrate
by spiralling
point
is almost
that
the Fe4
that accompanied
also
the structure honeycomb
3-36
thiourea-ferrocene
reflections observed
It was
seem to affect
A 3:1 crystal
was
The
these
by the ferrocene
disordered
and
cyclopentadienyl
electron
[12]. (IsO
K) and disordered
by K-rag
The structure .of the ordered phase was triclinic sixteen molecules in the unit cell on noncentred
with
crystallography. eight
sites-
The
of the
166 structure
the disordered
of
phase
was
found
that proposed in previous models [13]. of the mesophkse fqrm The structure
of
to
be
different
from
formylferrocene
(44-123" C) has been examined by Fioessbauer spectroscopy and-X-ray diffraction . The phase was found to consist of an orientationally disordered orFented
molecular at
mass-iron 3.
random
of 46 pm
STEREOCHHMISTRY A new method
absolute
through
of mass
on average, .~ with a centre of
[14]_
developed
assigned
for the determination
and optical
purity
stereorelating
The absolute
alkylferrocenes. (3.1) was
contres
were,
OF FHNEIOCENES was
co_nfiguration
derivatives
their
about
distance
The molecules
crystal.
of chiral
metallation
configuration
of the ferrocene
of ti-dimethylaminoof the aminoferrocene
[lS].
Fe
*
0 3.1
Cyclisation of g-ferrocenyl-a-phenylbutanoic the exo- and endo- -phenylferrocenocyclohexenones (3.3 and 3.4) were
The ketones
used
1,4-diphenylferrocenocyclohexenes absolute
and relative
to prepare
acid (3.2) gave (3.3 and 3.4). the pseudoasymmetric
(3-5, 3.6 and 3-7) and compounds
the
stereochemistries
of these
were
(3.8) was
by active ti-phenylethylamine The ketone (3.9) was treated
determined
c4. The racemic
and cyclized -Ath
phenylmagnesium
reduced
The
acid
to give
to
the
synthesis,
the ketone bromide
ferrocenophane
relative
resolved (3.9).
to give
the alcohol
(3.1-l) with
and absolute
retention
configuration
(3.10) which of
was
configuration.
and conformation
167
CH2CE2CO2H
0
Fe
0
3.3
3.2
3.4
Ph
Ph
Ph :
““3
:
0
Ph
Ph
3.5
of some methyl described.
substituted
The circular
carbocations were Fermentation glucose
solution
(+)-alcohol Treatment aluminium This
3.7
3.6
amine
curves
of various
reported [17]_ of ferrocene aldehyde-d resulted
(3.12)
was also
[3)-_(l,lf)-ferrocenophanes dichroism
with
in stereospecific
together
with
a small
metallocene
bakers'
reduction
amount
yeast
in
to give
the (3.13).
of the ether
of the alcohol (3.12) with bis(dtiethylamino)methane chloride gave (+)-N,N-dimethylaminomethyl-Id-ferrocene. readily
formed
a palladium
sodium tetrachloropalladate It has been shown that
complex
[IB]. the non-Saytxeff
on treatment dehydration
and
with
of
W-
ferrocenyl-t-carbinols to ferrocenglolefins is subject to stereochemical control in non-acidic media and in acidic media under Specific catalytic effects were not implicated kinetic control. Thus 2-ferrocenylin the determination of product stereochemistry. 3-methyl-2-butanol underwent
had
dehydration
the preferred with
neutral
conformation alumina
(3.14)
and
to form predominantly
3.8
___ --: c 3.9
H
1 :
I
:
H
I I
me_
---
Ph
3.11
!-
oI
0
H
Fe
Fe
I
0 *
3.12
3.13
OEG
169
-H20 Fe
3.14
the ferrocenglolefin acid under 3.16) with Cl9
3.16
3.15
kinetic
in which dilute
(3.15) while control
gave
dehydration
a mixture
(3.15) predominated.
hydrochloric
caused
with
trichloroacetic
of the olefins
Treatment
rearrangement
(3.15 and
of the olefin to the isomer
(3.15) (3.16)
I* The
(dimethylamino)methylferrocene
to the corresponding the dimethylamino formic
primary
group
with
was converted
(3.17; R = H) by displacement of SCH2C02H using thioglgcollic acid and
acid
as the reagent followed by treatment with ammonia, chloride and mercurg(II) chloride to form the product.
ammonium
The ferrocenylbutylsmine in asymmetrically
CHNR2
I
CHkIe2 Fe
3.17
References
(3.17; R = Ke)
amine
p_ 238
induced
(3.17; R = H) was used synthesis
[20].
as a chiral
template
170
4.
SPECTROSCOPIC
AND
orbital
A =olecUlW
carried
PH!fSICO-CHENICAL
and
(CNi30 and INM)
some
A semi-empirical was applied
molecular
to ferrocene.
the photoelectron
ionization
between
orbital
was
ferrocenes.
calculated
method,
p_
and
the PEEL method,
A consistent interpretation of both spectrum and the absorption apectrnm
The calculated
obtained.
calculations)
substituted
agreement was obtained spectra [21].
satisfactory
experimental
were
study
out on ferrocene
STUDIES
order
of the highest
occupied
(02,) ionization potential (a,g), orbitals, ionization potential agreed with experimental assignments in photoelectron spectra S.nd
the calculated electronic
The
and trimer
were
INDO series
structures
than
structures
orbital
molecular
molecular
bonds.
between
the metal
2px2pg
orbitals'of
INDO
transition
SCF
MO
metal
were
calculations sandwich
and the trimer StrUctUres
were
studied
orbitals
the major
Out
for
but
and the
contribution
significant
end the carbon
of the ligands carried
out
including
for
interactions 2s and
a series
of one extra
ligand
to the
[.2&j.
ferrocene
cobaltocene
in a dominantly
stable
was used
except
carried
bis(q-benzene) In all these complexes.
them by the addition
to reside less
were
complexes
its dimer orbital
ferrocene,
were weaker,
the 6-frameworks
The self-consistent method
made
[22]*
of the dimer
3d, 4s and &I orbitals
systems obtained from For all the complexes was predicted
rings
There
ValUeS
head-to-tail
calculations
including
of the ligand
metal-ligand
orbital
a Hueckel
and for some mixed sandwich the interactions between the metal
T-orbitals
generated
to the observed
the corresponding
of metallocenes,
complexes compounds
close
of ferrocenylacetglene,
using
head-to-head
stable SCF
were
calculated
me
treatment.
vere more
a
energies
the
level
of
electron.
extra
electron
and the species
than
the corresponding
d6 complexes
charge
and configuration
molecular
to compare
the electronic
(7-cgclopentadienyl)-(3)-7,2-dicarbollyliron
d6
and for
structures
and ferrocene,
[251. of
It
was concluded that the iron atom could bond to the open nearpentagonal face of the carborane in a similar way that it could bond
to
of.the seme dienyl r;llg WI-
were
ring except that the interaction However, these 6-orbFtals of the dicarbollide. the r-orbitals of the cgclopentasymmetry type as
a cyclopentadienyl
involveds-orbitals
171
A thermodynamic study of ferrocene were
obtained
the vapour
for
of temperature [27]. phase
of ferrocene
the Willis
wes carried
out. Equations as a function
of ferrocene
Molecular configurations in the disordered have been examined and interpreted in terms of This model
model.
an antiprismatic
pressure
molecule
permitted
of D
permitted
for the prismatic r _ independent 1281.
only one orientation for The two orientations
symmetry.
Sd molecule
of Dsh
symmetry
were
were investigated. Irradiation of ferrocene at doses of <2 x 10 15 protons gave only lattice defects but at doses of 2 - 5 x 10 15 protons polyferrocene At even higher doses metallic iron and Fe C were was formed. 3 Proton
radiation
formed [Zq]. Ferrocene
was
effects
suspended
in ferrocene
in epoxy
resin
and irradiated,
using
Moessbauer measurethe Van de Graaff accelerator, with protons. ments were carried out on the ferrocene sample after irradiation. It was
concluded
approximately behaviour
that
Fe3C was formed
100 g in size
and these
as ultrafine showed
particles
superparamagnetic
[3Oj.
Ferrocenyl-41-methoxganiline, ferrocenyl-&I-butylaniline, and dibenzyl-I,1 r-ferrocenedicarboxglate 191 I-dioctanoylferrocene were introduced into the smectic B liquid-crystal phase of z;b;;oxybenzylidene-bl-octylaniline.
These
systems
Fe Noessbauer spectroscopy at 'j'705;[31]. of human serum albumin with ferroceneFe and was
investigated A Hoessbauer
.ferrocene
Referencesp_ 238
by Moessbauer study
derivatives
was
[33].
spectroscopy
carried
were
studied
The interaction some iron
complexes
at 8.5 and 300° K
out on tetramethylene
[32].
bridged
Me
Fe
Fe
0
0
0
0
4.2
*
4.3
The fer?ocenophane
peroxides
0 4.4
(4.1; R = H, Me) have been
Fragments investigated by electron-impact mass spectrometry. were found to arise by thermal decomposition, rearrangement or loss of ethylene by a retro Diels-Alder reaction. The results obtained
were
sensitive
mass
spectra
to
the
temperature
of
the
inlet
system
r341. The (4.2,
4.3
and 4.4)
wex-e recorded
in the methylferrocene metal-ligand
bond
of methylferrocene spectrum
(Scheme
4.1).
and its deutero analogues The main fragments and inttirpreted.
formed by breaking of the
were It
was
shown
that
the
ions
C.,,H,,Fe+,
C6H6FeC, C5HSFe+ and C5H6Fe+ originated from a&isomerized form of the molecular ion in wnich all the hydrogen atoms were redistributed among
the ligends[jS].
C6H6Fe+
Scheme 4.1
173
Mass spectrometrg was used obtained from the electrochemical results
showed
present
could
that
to analyse
the concentrations
be determined
the product
alkylation
of
mixture
ferrocene.
The
of the alkylferrocenes
semiquantitatively
using
this
[36].
technique The
electronic
spectra
of two
series
of metallocenes
(M = V, Cr, Mn, Fe, Co, Ni) were (y-CSHS12M and (T-CSH4Me)2M For the V, Cr, Nn and Fe recorded between 10 and 50 x IO3 cm". derivatives
the charge-transfer
bonds
corresponded
only
to
) and for the Co ligandemetal excitations (e2n8 eig 2g' al& derivatives evidence was also found for metalyligand (e 1ge2u) me paramagnetic susceptibilities of these compounds transitions. were
also I,1
determined
and discussed
v-Di(chlorocarbong$
tetramethylpiperidin-4-01 (4.5) which were
was
consistent
internal
the
the two nitroxide joining
kcal mol
groups
the ground
were
with
2,2,6,6-
the ferrocenedicarboqlate The results
investigation.
with an activation energy -1 and with a conformation twisted
in the molecule
excited
condensed
to form
of a low frequency
and first
for the complexes
was
of an ESR
a species
C2
the two groups
The detection
N-oxide
subject
with
movement
[37].
errocene
out of the line
[38]. vibrational
electronic
[Ferricinium]fX-,
slightly
for in which
states
where
has
mode
coupled
to
been reported
X = tetrafluoroborate
and
The frequency of the mode in the ground state hexachloroferrate. was -84 cm -' and it was assigned to the y6 Raman inactive ring Intensities were discussed in terms of the torsional vibration.
Fe
4.5
Frank-Condon
factor
in the relationship
for the Raman
process
r393TheTf-electron density at the $-carbon chalcone
(4.6) was
and the‘value ferrocenes
determined
obtained
atom in the ferrocenyl13 C NMR shielding constants [ho]. NBB data for a series of
from
the
was 0.9297
and M-ferrocenylcarbenium
suggested
that
ions were
discussed. It was ion the cgclopentadienyl
in an oc-ferrocenylcarbenium
ring formed a fulvalene with the W-carbon atom which bonded to the iron atom via all six carbon atoms [4d Ferrocenes CEO,
CO$e, the first
bearing
electron
COMe underwent
one-electron
withdrawing
polarographic
step gave
groups
reduction
a radical
anion
in turn was such
while
the second
Controlled potential two-electron step gave a dianion. at the potential of either the first wave or the second cleavage iron. salts was
of the metallocene
group
The cyclopentadienide to form
applicability
The kinetics acid
in moderately
in the early
stages
A cell has been (633
efficiency
run)
caused
anions
transition
and metal
and tine reaction
of the protodeboronation that
sulphuric
the reactlon
of the protodeboronation which
in an ethanol achieved
of ferrocene-
acid were probably
proceeded
and that there was no indication in the electrophilic attack by a proton
to electricity
of 25 was
compounds
concentrated
described
semiconductor
of light
with
electrolysis wave
[42].
and mechanism
It was concluded investigated. by an 4 - E& 2 - type mechanism that the iron atom participated
based
combined
(T-cyclopentadienyl)metal
of general
boronic
to cgclopentadienide
anions
as CO2E,
in two steps,
employed
solution with
[a].
[43]. an n-type
silicon-
of ferrocene.
an output
Conversion
of 0.25 V and an
Ferrocenyltrichlorosilane
(h.7) was prepared by the addition of lithioferrocene to an excess of silicon tetrachloride. The ferrocenyl-silane (b.7) was attached directly
to a pretreated
platinum
platinum
electrodes
characterised
it was concluded hydrolysis
electrodes
thousand
100 mVs -' with material
that
ferrocene
of the silicon-chlorine
were
five hundred only
The derivatized by cyclic voltammetry aad
the electroactive
of one or more
derivatized three
were
electrode.
very
durable
cyclic
approximately
was
attached
The and in one experiment
voltsmmograms
via
bonds.
were
run
over
at
30% loss of the electroactive
[45].
The ferrocenyl-slime 1,l '-dilithioferrocene
(4.8) was prepared
to silicon
by the addition
tetrachloride.
An n-type
of
silicon
175
0
COCH=CHPh
0
SiCl 3
0
Q-l
0 Fe
0
*
lC1
0
Fe
W
'9,,
0
4.7
4=6
electrode and
to
was
treated the
dipped
with
silicon
the
into
photoelectrochemically
without which
5.
led
showed to
no
a rapid
REXCTIONS
OF
Electrolysis cgclopentadrene
of and
o*o ago 5.1
Refezencesp.238
sodium
hydroxide,
which
surface
became
attached
reduced
and
waves
decline
of
and the
covalentlg ferrocene
oxidized
Whereas
deterioration.
cyclic
washed,
a build
dried linked
was
forms
nonderivatized
up of silicon
photocurrents
cycled
repeatedly
dioxide
C461=
FEBROCBiGS
+
Fe
(4.8)
The between
any substantial
electrodes
aqueous
silane
surface.
4.8
a solution lithium
containing
bromide
between
dimethglformamide, an iron
anode
and
a
176
nickel
cathode
gave
ferrocene
in a current
yield
of 88%
‘[43’].
A series of labelled
ruthenocenes was prepared by heating ferrocenes with '03Ruc1 . For example, benzoylferrocene were heated at 180~ ro2 anproximately half an hour to 3 give benzoylruthenocene, ruthenocene and I,? *-dibenzoylruthenocene. -M'nena mixture of acetylferrocene- 59 Fe and ferrocene methylcarsubstituted and '"?RnC1
boqlate
was heated
of labelled
The ligand ferrocenes
with
dimethylferrocene derivatives isolated
in the presence
ferrocene
derivatives
exchange coronene
of iron(II1)
chloride
obtained [&a]. ferrocene and some substituted reactions of Ferrocene and l,l'were investigated.
underwent
(5.1; R = H) and
exchange
to give
the ?-coronene
(5.1; R = #e) respectively
as their hexafluorophosphate
salts
which
[49].
.+
Fe
2-k
5.4
a VaI'ietY
was
were
177 Ferrocene
underwent
dimethylanthracene aluminium
mixture
hydrogenated and
endo.
was
used
(5.2
and
ligand from
in in
in
the
5.4)
exchange
(5.2)
and
form
where
the
aluminium. at
an the
ligand
were
exchange
had
The
obtained.
between
the
underwent
The
and
reaction
i-
reflux
cation
ligand in
two
reactLon,
(5.2) excess
been
with
9,10-
added
(5.5) and
was
products formed
ferrocene
or
of
by directly
[SO].
wit‘n phenanthrene
presence
aluminium
Q
and
chloride
9,10-dimethylphenanthrene gave
the
mononuclear
+
0
&
5.6
-I-
Fe
cis
(5.3)
isomeric
ferrocene
exchange
the
temperature
dication
Fe
p_ 233
with
chloride-
stereospecifically
hydrogen
0-O
References
reaction aluminium
cis-9,10-dihydro-9,10-dimethylantbracene
9,10-dimethylphenanthrene
cyclohexane
of
to
9,10-dimethylanthracene Ferrocene
exchange
presence
decalin
product When
a ligand
the
in cation
(5.6)
1'78
.Q .A3
Q 0
co ‘CH2 +&co-
Fe
CO(CH )
0
0
Fe
Fe
0
A’
0
n
5.11
5.12
CO (CH2)4C02H
Fe
Fe
Fe
CO (CH2 14C02H
5.14
5.13
Fe
Fe
Fe
24
co
H
2
179
and the binuclear products addition, were
(5.7).
cation
vlalogous products
Exchange
to those .obtained with where
the mononuclear
hyorogenation
cation
(5.8)
with
phenantbrene
phenanthrene
accompanied
gave
but gave,
exchange,
these
dication
(5.9)
and the binuclear
CN* A series possibly
by treating presence istered
with
ferrocene
to rata
C
with
l-4
(5.10; R = CS_7 cgcloalkenyl
al%&
Ph, CH2Ph,
the appropriate
acid
Cl) was prepared chloride
Some or' the scylferrocenes
of a catalyst.
Ferrocene presence
of acglferrocenes
substituted
were
acylated
of aluminium
with
chloride
isononanoyl
to give
chloride
Fe
0
in the
Fe
0
I Fe
0
.*_
admin-
(trimethylhexanoyl)ferrocene
153 I-
5.16
in the
[.52]. was
*
5-n
0 5.18
180
Femocene the.presence
alkylated with methylmonochloroacetate
was
of aluminium
chloride
to give methyl
in
ferrooenylacetate
The acetylation of ferrocene with acetic anhydride has been [%]reported using as catalyst magnesium haiides (chloride, bromide and iodide)
in the form
of the etherates
The Friedel-Crafts has
been
methylenedichloride reported 5.13)
together
with
formations
using
In addition
four
(5.14 and 5.15) secondary
The reaction
of ferrocene
in the presence
ferrocenylalcohols
monoacylated
which
compounds with
predominant,
chloride and
(5.12 and
were
arose
obtained
by trsns-
[56].
1,6dioxaspiro[&&]nonane
of trifluoroacetic
(5.17 - 5.20)
adipoyl
as catalyst
to the previously
ferrocenes
products
formed
[ss].
with
chloride
(s-11), both
product
of the first
(5.19) was
of ferrocene
aluminium
as solvent.
polymeric
and diacylated
(5.16)
acylation
reinvestigated
in benzene
acid
in which
the mechanism
gave
a mixture
the binuclear
of the reaction
of
diol was
discussed
c-5.71. 6.
F'EIEzRICINm The
SALTS
crystal
and molecular
tetrafluoroborate
(6.1) has been
The diferrocenyl
cation
has
determined
for diferrocenyl
were
to be bent
found
the two iron and 2.81
atoms
stabilization interaction
ketone.
It was concluded
from metal-exocgclic
and to delocalization shifts
spectroscopy.
Shifts
ion have of both
that
carbon
distances
reduced
the distorted and that
attributable
charge
been
determined
by 1%
and negative
to such
[58].
perdeuterometallocenes
positive
rings between
to 2.69
interaction
ions was
of positive
in paramagnetic
the perdeuteroferriciniu
were
that
to
ferrocenyl
so that
carbon
crystallography. similar
substituted
atoms
of CGferrocenylcarbenium
Isotope
by X-ray
conformation
The
and the exocyclic
resulted
of o<,oc-diferrocenylmethylium
determined
a transoid
at the &-carbon
g respectively.-
structure
structure
including NMR
sign were
observed
and a large dipolar shift was observed for the perdeuteroferricinium ion. The isotope shift increased with the number of unpaired electrons and with the efficiency of electron delocalisation LWThe mixed valence cations of biferrocene and biferrocenylacetylene (6.2) were formed from the neutral ferrocenes using [(2,2~-bipyridine)2Ru.PPh3.C1](PF6)2 cations
displayed
to intervalence
near-infrared transfer
as the oxidiaing
absorption
transitions
bands
between
which
isolated
agent.
The
were
assigned
Fe(II)
and
181
Q
+
0
Fe
0 0
CH 4
0
0
BFk-
Fe
~
0
~
6.1
Fe(III)
sites.
4.2
The energies
functions
of the dielectric
with
theory.
Hush
iron separation valence cations transfer
optical
6.3
constant
The energies
in the cation. have localized
properties electron
of these
were
transfer
were
were
correlated
of the medium also
It was valence
consistent [60].
bands
concluded sites
with
used
correlated that
with
in accordance
with
the iron-
the mixed-
and the intervalence
the Hush
treatment
for
182
of the neutral
-_-Oxidation
benzene
while,
both
atoms
through
ferrocenes
Q
indicated catalyses
me
of native initial
state.
strong oxidation
Fe+
rates
CH2CH2R
6.5
BF -.
4
6.6
atoms
ferricinium
and maximum
that the two iron electron
in the cation
The magnitude
r611. of ferrocene
or immobilized
iodine. in
in intramolecular
interactions
T-system
with
and the averaged-valence
indicated
the two iron
0
6.4
(6.2)
involved
oxidation
to the corresponding
in the presence studied.
in contrast,
the conjugated
The enzyme
cation
spectroscopy
(6.2) were
in the same
rupole.splitting
ferrocenylacetylenes
valence
Moessbauer
in the cation
transfer were
the mixed
(6;3).
cation atoms
gave
between and
(6.3)
of the quadthe iron
some
substituted
ions by -hydrogen peroxide
horseradish of oxidation
peroxidase were
was
determined
133 and It was found hydrogen
that
peroxide
the rate
of oxidation
concentration.
horseradish
peroxidase
the absence
of any added hydrogen
A series were
ferrocenes decrease
in a coupled
system
peroxide
Compared
the infrared
intensity
glucose
by
otidase
in
[62]. and their
to the analogous
spectra
of the
also oxidized
hexafluorophosphates,
(n = 0 - 5), was prepared
recorded.
in band
was with
of sgm-polymethylferricinium
(Me,C5H5_n)2FeefPF6spectra
was independent
Ferrocene
of the salts
displayed
for C- H stretching
infrared
sgm-polymethyl-
modes
a marked of the methyl
Whereas, the intensities and the frequencies of the groups. corresponding bands for the ring M stretching modes were higher
[631The reaction with
of sodium(dicarbonyl)(I_cgclopentadiengl)ferrate(-l)
the ferrocene
derivatives
(6.4; R = E-MeC H SO , Cl) gave
2-ferrocenylethyldicarbonyl(?-cyolopentadienyl(i~on3(6.~). of the latter ferriciniura Reaction gave
compound
salt
(6.5)
with
Reaction
salts
of the dicarbonyliron the cationic
released
from
the complex
hydroxide
(6.7) with HBF4 or Et30BF4 R = H and Et) respectively. (6.8;
(6.8; R = H) with diazomethane gave the methylated derivative (6.8; R = Me) [6S].
gave
iodide,
sodium
or sodium
complex
complex (6.10).
(6.9) with ferrocenylFerrocenylethylene was
(6.10) on treatment
trlfluoroacetate,
borohydride
sodium
with
triphenylphosphine,
cyanide,
sodium
[66].
BP -
Fe
4
6.7
References
the
salt
ethylene sodium
gave
of the ferrocenyl-ketone
of the
corresponding
tetrarluoroborate
[64].
the tetrafluoroborate
Treatment
trityl
Treatment
p_ 238
6.8
+Q
184
Q 0
Fe-l/ (co)2
f
0
Me C2
BF
4
-
2
zh,
CH2
iCH
0 0
BF -
4
Fe
6.9
*
0
6.10
Oxidation gave The
the
reaction
presence
of
ferrate(II) being
of
the
corresponding
formed
of
the
potassium and
the
borinato-iron
complexes
ferricinium
derivatives
ferricinium
hexacganoferrate ferricinium
[68].
Q 0
Fe
6.11
ion
6.12
ion
with
(6.11;
hydroxide
gave
R = Me,
(6.12) ion
potassium
decomposed
without
Ph)
[67]. in
the
hexacyanoany
ferrocene
185
6.13
The
thermal
ammonium and
decompositions
perchlorate
and picrate
ethylenediferriciniu
The mechanisms Complexes transition
ion-ferrocene
p-diketonate
cyanide, changed
system
were
acetone,
and
(6.13)
[TO]
isopolgacid
determined varied
of the acid
and the quantity
were
studied.
anions.
cation
and
Amino-
in some acidic
betueen
(hydrochloric, of the organic
solvent
dimethylformamide
alcohol,
aqueous-organic
+O.l - to.66 V as the sulphuric and perchloric) (acetic
and
acid,
methyl
dimethylsulphoxide)
[72].
Cyclic of oxidation organic
and I,1 I-diethylferricinium
in complex formation with transition The electrode potentials of the ferricinium
The potential
concentration
[69]
perchlorates
ferrocenes also took part metal thiocganates [71].
changed
(ferrocen~lmeth~l)dimeth~l-
of the decompositions were discussed. have been formed between the ferricinium
metal
solutions.
of
voltannetry
solvent
perchlorate. the reaction
has been
of ferrocene mixtures
Rate was
containing
constants
found
used
to investigate
to the ferricinium
acid-
0.02 fi tetraethylammonium
for the oxidation
to involve
the mechanism
ion in aqueous
a fast
were
protonation
obtained step
and
followed
by a change from solvated ferrocene to hydrated ferricinium ion. The instability of the ferricinium ion caused the reaction to be Changes in the nature and concentration Of quasi-irreversible. the mineral-acid
and the organic
of the ferrocene-ferriciniu manner.
These
Refereneesp.238
controlled
solvent
ion couple changes
caused
the redox
to change
together
with
Properties
in a controllable
complexation
of
186 meta-l cations oxid+
formed
the presence
in
Denisovich
of a second
in anode
the ferricinium
of a method
co-workers
and
formed
radicals
the basis
potassium
that
decarboxglation
one
the interaction of carboxglate
the same electrode
at
of dkylfsrrocenes.
formation
deteddng
[73.].
found
generated
iOn
fop
led
of anions
with
to the
For example, the electrolysis of a
acetate,
acetic acid and ferrocene gave a mixture of methylated ferrocenes. A similar reaction of the or their ferricinium ion with radicals generated from dibasic &ids nzitiure
half
of
esters
It was
gave
shown
esters
of ferrocenyl
that the orientating
the same for radical electrophilic
substitution
substitution
containing
effects
in the ferricinium
of the corresponding
derivative c741The ferrocene-ferricinium
cerboxylic
cation
system
function mixtures of
was a better
standard
proton
have
galvanic
mange2
been
in
determined with
cells
measure
has been
little
ratio
effect
alcohol
7.
PRRROCEXYL CARBENIUM IONS The alcohols (7.1; R = 11, Me,
heterolysis acid
(exo-departure
to give
the
ol' the
the corresponding by rotation
diastereoisomer
equilibrium
mixture
exo-protonation
alkylium base
ions which
to form
isobutyl [7s].
Ph) underwent which
and
7.3)
underwent
[76]=
stereospecific
equilibrated quenched
with
bond.
its
When
aqueous It was obtainedunderwent prefer-
wwe
(7.2 and 7.3)
3-n trifluoroacetic
on
OH) in trifluoroacetic
the ferrocenyl--Ci
of the cations-was
group
acid
with
to give ferrocenyl-
exo-deprotonation
in the presence
of
[77].
Ferrocene acid
measurements electrodes.
affinity
protonated
cation
about
sodium carbonate the alkenes (7.2 shown that the alkenyl-ferrocenes ential
function
proton
[75].
and water-ketone
or in the hydrocarbon
on‘the
the
to deter-
end The Pleskov
of the solution
of water-alcohol from acidity
ferrocene
used
platinum-ferrocene-ferricinium
the water-alcohol had
of the acidity
affinities
were
ion as for
neutral
mine Hemmet and Pleakov redox functions in propanol-water iso-propanol-water mixtures containing perchloric acid. me
acids.
of the substituents
was
as a stable
with
isobutyraldehyde
I-ferrocenylisobutanol
carbenium
The
treated ion
which
gave
and trifluoroacetic the ferrocengl-
the reaction conditions used ion..(7.5) was obtained ferrocenylbenctrotrenylcarbenium violet-blue
(7.4)
under
fluoroborate.by
treatment
of the appropriate
Q 0
ccc
I:
0
NPh 'Me
Fe
Fe
0
7.1
7.2
Fe
7.3
Fe
7.4
carbinol
7.5
with
fluoroboric
acid in propionic
Treat-m-at of ?,3-diferrocenylallgl 3-ferrocenylallgl gave
the catFons
(7.6) with
alcohol
with
(7.6 Pnd 7.7)
N,N-dimethylaniline
(7.7) underwetit a skilar
alcohol
ffuoroboric
anhydride
and I-methyl-1-c~~trenylacid in acetic Treatment
respectively. gave
reaction
[79].
the olefin
snhydride
of the cation
(7.8), the cation
[SO].
A
mechanistic study was carried out on t&e fragmentation of ferrocenyldiarylmethylix~m ions in aqueous acidic methyl cyanide. For example,
the cations
the corresponding formation
References
p. 238
orthe
fulvenes
(7.9; AZ = Ph, E-anisgl) (7.10)
alcohol. precmsors
tog&Aer (7.11).
wFth
fragmented repeated
to give
reversible
-Changes in acid
strength
188
7.6
Fe
*
7.7
Fe
1,
0
0
7.8 and substituent amino)calicene form
effects (7.12)
the dicyclopropenium
potassium
were
investigated
was heated complex
with
[al].
iron(Iii)
(7-33) after
s,&Bis(diisopropylchloride
in
the addition
THF to of
perchlorate
[a23. The acid-catalyzed hydration of ferrocenylacetylenes with alkyl substituents in the 2-, 3- or 1’ -positions has been subjected to a kinetic study. The reaction involved the formation of an intermediate vinylcarbenium ion (7.14) and gave acetylferrocenes as the products [833. from
Comparison of the pKR values for the carbenium the ferrocenylcarbinols (7.15; R = H, 1Ge) with
ions derived t'nose for
the
189
Ph OH
7.10
7.9
7.11
N(CHNe2)2 Fe
2ClO N(CHMe2)2
N(CHKe,),
7.12
Q
&CH2
0
Fe
7.14
References p_ 238
7.13
4
-
7.16
7.15
chromiumtricarbonyl demonstrated
complexes
that the ferrocengl
the chromiumtricarbonyl _
group _
(7.16; R = H, Me)
of the carbinols group
was much more
in stabilizing
efficient
the adjacent
than
carbenium
ion [84]. 8.
FERROCENE
CHEXIST~Y (i) Photochemistry
.The unsaturated with
ultraviolet
acids
light
at pH 9 in the presence and the corresponding chemically
reduced
(8.1; n = 0.1 and 8.2)
of wavelength of nitrous ferricinium
back
ions were
to the original
produced
acids.
Q
cdco2H
0
*
0
8.1
were
irradiated
240-250 nm in aqueous solution Photo-oxidation occurred oxide.
8.2
which
It was
could
thought
be
that
Q .Q
cH2c02- : .-
FS
*
CH2CO2-
.hv Fe
0
*
0
0
0
8.5
8.4
8.3
OH-
-/ OH
S%
CH2CO2
I Fe
6 0
8.6
oxidation occurred by electron transfer to nitrous oxide from a photo-excited state of the acid c85l. The photochemical excitation of the ferrocenyfacetate (8.3) and ferrocenoate anions gave, in each case, an excited state (8-k) which
transferred
an electron
to nitrous
oxide
which
acted
as an
electron acceptor. The lifetimes of the excited states were 2ps and O,O?ys respectively. The product of electron transfer from the excited stat,e of the acetate (8.3) was. -the zwitterion (8.5) w?nich with,base
was
thought
(y-cgclopentadienyl)%ron ethanol _ferricinium
to form
complex
the
(a.61
(q-cgclopentadiene)[86].
solutions of octamethylferrocene and octamethylhexafkorophosphate were irradrated with incandescent
192
40-500 u
lamps.
of the solutions absorption
A periodical
variation
was
throughout
spectra
observed
studied
(210-800
increased with the concentration that an oscillating photochemical
in the optical the rsnge
nm).
density
of electron
The period
of variation
of the solution. It was suggested redox process was being observed
Ca7 1. Carbon tetrachloride and other halogen0 compounds with a similar or higher electron affinity underwent photoinduced dehalogenation in A chain alcohol in the presence of ferrocene or iron(iI1) chloride. propagation
mechanism
was used
to explain
the high
obtained which was >6 for carbon tetrachloride. acetate was monodehalogenated in low quantum yield it had a high electron affinity [88]. Copolgroers of methyl ethyl
methacrylate
have
methacrglate
been
photosensitizers acid
evaluated High Red A.
and Fast
methacrylate of Perrin's excFted both
synthesized
The quantum
model
quenching
though
with
l-ferrocenylas
and t-heir efficiencies
low quantum
changes
quenching
ferrocene
interaction
nearest-neighbour
caused
yield
for static
arzd ground-state
even
for the redox reaction between L-ascorbic proportions of I-ferrocenylethyl
in the copolymers
sensitization.
or styrene
quantum yield Methyl trichloro-
yields
discussed
for in terms
interaction between adjacent It w2.s considered that
groups.
and energy
ferrocene
were
groups
migration
with
occurred
the former
between
assuming
more
importance than the latter [ 891. The quenching of [U02]2f emission by ferrocene, some substituted some substituted ruthenocenes and osmocene ferrocenes, ruthenocene, has
been
investigated.
of the excited obtained
both
The values
state from
a quencher, 10%
reduction
by iso-propanol of local
it was concluded
was negligible [913.
within
in the presence
that
quenchers
were k -Q measurements. potentials
transfer
mechanism
[90].
of benzophenone
concentrations
strong
the oxidation
an electron
vinylferrocene-VinylbenzoPhenone
the presence chain
supported
were
constants
and lifetime
with
(U022+)r- and the metallocenes
benzophenone) of
intensity
correlated
and this
The photochemical and
and the quenching
luminescence
k were of loglo--&
of the metallocenes between
All of these metallocenes (U022+)"
and absence
copolymer of ferrocene,
energy
the triplet
and poly(vinyl-
migration lifetime
was
of ferrocene
studied.
In
which
behaved
along
the polymer
(approximately
as
193
(ii) Derivatives Ferrocene
containing
Gas metallated
tetramethylethsnediamine sodioferrocene yields
after
yields
were
other metals
(TZE!DA) to give
in the ratio
(metalloids)
by n-pentglsodium
I,?'-disodioferrocene
The reaction
9:l.
in the presence gave
near
In the absence 1 hour at room temperature. and polymetallation products were also
lower
of and
quantitative of TIGDA obtained
c94* The reaction between a-butyllithium and potassium(-)(lR)menthoxide gave n-butglpotassium w‘hich was used to metallate ferrocene. The
l,lr-dimetallated
obtained
ferrocene
in 74% yield
n-butyllithium
[93].
in the presence
(PICDT) in the molar
ratio
was t'ne predominant
The metallation
both
a dilithioferrocene which was The 'H by 'H IWR spectroscopy and X-ray analysis. was temperature dependent in benzene and toluene solution The solid cyclopentadienyl and base exchange taking place.
I?< :
r-4
-qlpfjj \ :
Fe
Fe
8.8 Fe
8.7
References p. 238
and was
with
of pentamethyldiethylenetrismine
l-3 gave
investigated zII.3spectrum with
product
of ferrocene
194 complex
[(q-CsHk)2Fe.PWT.Li2]2
soloated bound
md
unsolvated.
to the three
lithiums between
(8.7) had two types of lithium The solvated lithium atoms were each
nitrogen
.partTcipated
atoms
of the P&KIT while
in a four-centre
the two ferrocene
electron
atoms
the unsolvated
deficient
briQe
grollps.
The lithium-iron distance was short (2.667 g) which indicated bondin g between the lithium-and a ferrocene e molecular orbital [94]. Phenylgazoferrocene was mercurated to give a mixture of 2-chloromercuri(phenylazo)ferrocene (8.8; X = H&l) and bis(2phenylazoferrocenyl)mercury. by iodine yield
Both
to the 2-substituted
of the compounds
iodoferrocene
were
converted
(8.8; X = I) in high
[S].
ferrocene derivatives (6.10; R = Ne, Et, CN, CONe, trifluoroacetate gave high yields of the corresponding mercurated derivatives (b-9 1. The mercurated compounds (8.9 ) were converted to the halofeProcenes (6.10; X = b, 1) by reaction with potassiti-trdbromide a-?d potassium triicdide / respectively [96]. Treatment
GHO;X
=
H)
of- the
with
me~c~~g(1I)
X
Hg(02CCF3) (F3CC02)Hg
0
* (F3~~02)~g
R
Fe
Hg(02CCF3)
Fe
Hg(02CCF3) 8.10
8.9
The ferroceayldihaloboranes (8. II; K = Cl, Br, I) were prepared with the corresponding by the reaction of ferrocenylmercurichloride The infrared spectra of the ferrocenyl-boranes trihalide. and "E-X (8.11; X = Cl, Br, I) wnre recorded and the 'O-X
boron
stretching
frequencies
were
Ferrocenyldibromoborane
(8.12) to give was characterized
assigned
[97].
combined
with
the
distannacyclohexadiene
the diferrocenyldiboracyclohexadiene as
the
nickel
complex
(a.141
[98].
(8.13) which
195
Q 0
BX2
Fe
Me2Sn
/=l
SnMe2
U
6
0
-
8.12
8.11
The thiodiborolene
(6.15)
was
treated
and bis[dicarbonyl(?-cyclopentadienyl)iron]
with manganese to form
carbony
the triple-
decker mixed metal complex (8.16). This product (8.76) gave a cationic complex with aluminium cbJoride which ~2s in turn pyrolyzed to yield the neutral tetra-decker complex (8.17) [99]. R1R2Si(C=CH) The hydrosilylation of silglacetylenes, 2' uhere R' = R2 = Et Ph R1 = Ne R2 = Ph, with the ferrocenylsijane (8.18) UsingaSpki~r's'catalyst'gave the products (8.19; R1 = R = Et, Ph, R' = Me, R2 = Ph) which were formed according to Farmer's rule
[IOOJ. Reaction of c+naphthylferrocenylmenthoqsilane with boron t&fluoride etherate gave the bifunctional enantiomeric silane Treatment of the ferrocenylsilane (8.20) with palladiutn(II) (8.20). Treatment of the chloride gave the fluorochlorosilane (8.21).
8.13
Refemmsp.238
8.14
196 S
__B’
‘B-
J-4
Et
Et
fluorosilane (8.20) with Grignard reagents and organolithium compounds resulted in selective replacement of the fluorine In these
reactions
there
was retention
of configuration
with
atom. the
organolithium compomds and a mixed stereochetistrg was found When Grigna.rd reagent was used in solvents wTth Grignard reagents. with increasing basicltg the stereochemistry changed from inversion
SLHPhNe
Fe
SiPhMeCH=CH-
Fe
0 0
8.18
_o 0
8.19
SiR'R2
197
Q 0 0
P ---Si----H
Q 0 0
GNP
Fe
7
---si ----c1 a-Np
Fe
0
0
a-Np
= W-naphthyl
8.21
a.20
to'retention. reagent
whilst
attack
[lOI].
acetylene
Inversion retention
was the result of axial attack of the was explained in terms of an equatorial
Monosubstituted
combined
with
acetylenes
trisubstituted
including
silanes
ferrocenyl-
MePhSiHH
in the
presence
ofSpeier's catalyst to give one of two possible regio, where and MePhR'SiCR2=GH selective products MePhR'SiCH=CHR2 *I = R2 = ferrocenyl, R' = cymantrenyl, R2 = Ph, SiPh3 f 102 3 . Ferrocenylacetglene was lithfated and the S-lithio intermediate treated
with
trialkylchlorogermanes
(8.22; R = Me, Et,
Ph) and with
the diferrocenglgermvles (8.22 and 8.23)
(6.23; R -
were hydrogenated
CsCGeR3
Fe
0 0
8.22.
to form
8.23
the germylferrocenes
dialkgldichlorogermanes He,
E-t,
over Raneg
Ph).
These
nickel
to form products
but were
not
198
Q
SiHIqeR
SiMeRCH=CHCMe20H
0
Fe
*
HCGCCMe20H
+
-b
Fe
0
*
8.24
8.26
8.25
reduced
by palladium
powerful
enough
on calcium
to reduce
ti-Hydroxyacetglenes silanes
to form vinyl
carbonate,
underwent
silanes,
hydrosilation
(8.25) to give
the product
reaction
was
the presence
l8.26;
R = Me).
by the nature
of H2PtC16;the
following
with
reaction
with
is
ferrocenylthe
the hydroxgacetylene SimLlar
reactions
The relative
l,l-disilylferrocenes.
determined
which
[103].
In a typical
(8.24; R = 14e) combined
out with
a reagent
silglacztylenes
dimethylsilane carried
0
rate
of the ferrocenylsilane order
of reactivity
were
of the and
was
observed: (8.27; R = Me) >(g.Zk ;
Q
R
=
Me)>>(8.&;
R = Ph)B(8-27
SiRNeR
0
3%
Fe+
SiFIMeR
8.27
8.28
': R = Ph)
[104-j.
199
Complex
formation
investigated. iodide
ions
in ether
x = Cl, Br, I). while
by diferrocenyltin
The dichloride
combined
at -40" to form
A I:? complex
a 1:2 complex
was
formed
Diphenylchlorophosphine presence
with
between
the phosphine
treated
chloride
COBu)
COMe,
(E-30) where
were
the ligand
with
to form
been
cymantrene
prepared
[?Os].
ferrocene
obtained with
(6.28;
in the
ferrocenyldiphenylof benchrotrene
by direct
the loss
together
with
L was triphenylphosphine,
reaction
of csrbcn
analogues
diferrocenylphenylphosphine
diphenglphosphine,
salts
and
dimethylformamide
derivatives
and the complex
The monosubstituted
monoxide. Et, CSH,,,
phosphine
have
with
bromide
dimethylsulphoxide
Ferrocenylphosphine
phosphine [106]a and substituted cymsntrenes
has been
chloride,
the ferricinium
was formed
was
of aluminium(III)
dichloride
with
(8.29; R = h, the benckeotrenes ferrocenyl-
or triferrocenyl-
[107].
Q
:: CH2P~2
0
Mn
(CO)2L
8.30
8.29
A mixture phosphine
of two
oxide
complexes
cgclopentadienyl)iron oxide
(8.31)
Me02CCH2CH2COC1
acid
oxides
with
dicarbonyl(q-
the ferrocenylmethylphosphine
gave
of ferrocenylphosphines
has been
reported.
chloride
using
aluminium
the diferrocenylphosphine
two reduction reduction
products
product
with
and
A typical
of diferrocenylphenylphosphine
in methylene
to give
and a third
References p_ 238
treated
to give
of a number
the treatment
as catalyst
diphenyl(cyclopentadienylmethyl)-
[108].
ferrocenylphosphine
This product
was
dimer
The preparation involved
isomeric
8.31
with sodium
(e-32)
synthesis
oxide
with
chloride in 70% yield.
zinc and hydrochloric borohydride
[109].
-
200
Q
Q0
R2 hHP(O) (OR1)2
0
Fe
Fe
COCH2CH2C02Ne
8.32
8.33
The
condensation
HP(0)(OR1)2
of formylferrocene
(RI = Me, Et, CI-Die2)gave
(6.33; R2 = OIi).
hydroxymethylphosphonates
(6.33; R2 = OH) were anhydride esters
to give
treated
an amine
with
of either
in It'nepresence @4eC6RkNH,
Q 0
ferrocenyl-
phosphonates end acetic
(8.33; R2 = I4e) and
or acetylferrocene
phosphonate
p-02BC6HkNR,
gave
(8.34;
with
the cor-
R' = H, Me;
mor,holino, piperidino; The antimicrobial activity
Bu, Ne2CHCH2). was
investigated
b(O) (OR3j2
R'
[II?].
-e
A2
Fe
2
0
0
8.34
P
kf
Fe
0
T"ese
sulphate
of a dialkylphosphonate
R2 = PhXi,
compounds
ethers
formylferrocene
ferrocenylaminomethyl
R3 = ke, Et, Pr, Ne2CH,
the phosphonates
[IIO].
responding
of al1 these
dimethyl
the corresponding
(6.33; R 2 = COMe)
Treatment
with
the corresponding
8.35
6.36
P
201
8.38
8.37
(8.35) was heated with iron(I1) (8.36) as a stable red
Dimethyl-3,4-phospholyl-lithium chloride solid.
to form
A tetraphenyl-I,1
way
same
the I,?'-diphosphaferrocene
I-diphosphaferrocene
was formed
[112].
A convenient been
reported.
with
1
synthesis of dimethyl-3,4-phosphaferrocene has (T-Cyclopentadiengl)dicarbonyliron dimer was heated
-t-butyl-3,&-dimethylphosphole
(C.37) in 38% gave
carbonyl me
Treatment
yield.
the phosphorus
ferrocene
sulphones
(T-C5H,+CH2)Fe(q-C5H5), prepared
from
the
to give
of
the
complex
the phosphaferrocene
product
(8,38)
with
S02R2
CH2CH2CN,
CH2CR2C02z9
corresponding
sulphonic
0 Fe
0
CR(OH)C6Hq1ale2 3 were
acids.
CHRS-
Y
0
8.39
p_ 238
nona-
[113].
0
Fe
diiron
C8.39; R' = E, Me; R2 = H, Na, Nxt2,
R'
References
in the
2
8.40
Sulphonation
of
-202 methylferrocene lead
salts
combined
with
sulphur
and di-sulphonic
of mono-
trioxide
acids
in dioxane
which
were
Ferrocenylmethanol
[Ilk].
-w%th di-fuxxotional
gave
separated
a mixture as their
and 1-ferrocenglethanol
mercaptana
HSYSH,
where
Y = CH2CH2,
CH2CH2CH2, CH2CHMe, (cH2~H2120, (cH2~H2)2~ to give the corresponding (8.40; R = H, Me) [lls). sulphides Phenylferrocene by aluminium(II1)
treated.with
chloride
(8.41)
c'hromium complex
Cr
Fe
was
and
which
chromium(IIi)
aluminium was
to form
characterized
chloride
the bis(T-bensene)_ -
8.42
Ethynglferrocene was treated with &-PtC12(PMe2Ph)2 the complex trans-PtC1[C=C(C5H~)Fe(C5H5)](PMezPh)2 which in methanol
(8.42) rather ion
than
to give
a plat;inum stabilized
the alternative
ferrocengl
to form underwent
carbenium
stabilized
ion
carbenium
[117]. Diferrocenglme&curg
acid
[116_1.
as the iodide
Fe
8.41
protonation
fo1lowe.d
was
treated
with
MeAuPPh3
the ferrocenylgold complex
in THF to form
and fluoroboric
[(q-CsHs)Fe(y-C,$Q)-
(_LuPP~~)~ ]BF, [I181. 8.
(iii) Complexes
of ferrocene-containing
l,l'-Bis(diphenylp*hosphino)ferrocene bidentate
ligsnd
towards
transition
ligands has
metals.
been
evaluated
Complexes
as a
containing
(8.43; M = CoC12, cobalt, nickel and copper halides were obtained CoBr2, Co12, NiC12, NiBr2, Ni12, GUI) together with three tetraThe ferrocene ligand carbonyl complexes (8.44; M = Cr, MO, W)was found ethane
to behave
[I1 93.
in much
the same way
as bis(diphenylphosphino)-
203
Q\ PPh2
0
!=f
Fe
/ 0
Q 0
I
kPh2
0
Ferrocenoylacetone (8.451, HL, has been used as a bidentate ligand to forx the complexes VOL2, CrL3, EnL2, CoL2, NiL2, Cti2. The complexes were characterized by spectroscopg and the ML2 complexes underwent thermal degradatZon in a single stage remf;ion w%th the exception of CuL2, R 20 which was degrsded by a two-stage process [120f. Titanium polyferroeene oximes (5.46; R = Ph, Ma) were prepared by the reaction of'bis(~-cgclopentadiengl)titanium dichloride with the appropriate oxime in the presence of excess base. The polymers and by (8.46; R = Ph, I&) were malysed therzuogravimetric~J..Ilg
0 0
Fe
n
S-45
iteferen-
p.228
8.46
,
o- P 0
0
Fe
Nb
,*0
0 0
i2
8.47
differential by similar 180~
scanning exothermic
and above
Tine polymers of their
this
began
weight
Reaction
calorimetry. routes
temperature to degrade
up to 600s
Thermal
in nitrogen they
occurred
at about
chloride
by Noessbauer
Q 6:
spectroscopy.
~=PI(CO)s
0
OEt
Fe
0
8.48
to form
paths.
retained
50%
[?21].
of dichlorobis(q-cgclopentadienyl)niobium
the carbynes (8.49; H = Cr, NO, .Acetylferrocene thiosemicarbazone
iron(11)
occurred
by different
250° but they
ferrocenyilithium gave the. ferrocengl-niobium derivatives (8.48; Treatment of the ferrocenyl gave
transitions
and air up to approximately
the
W;
with
complex (8.471 [122]. M = Cr, MO, W) with
X = Cl, Br, 1) [123]. has been treated with
complex (8.501 which was characterized In the same way l,l1-diacetylferrocene
0 0 0
Fe
0
8.49
G=M(co)4x
BX3
205
Fe
Fe
0 0
8.51
8.50
0 0
8.52
6 0
8.53
206 thiosemicarbazone
gave
The reaction c1*3. diferrocenylacetylene A similar
reaction
a polymeric
structure
gave
between
the mixed
carbon thr88
of the latter
of 1.462 A but
length
atoms
being Th8
atoms.
the eclipsed obtained with
salts
125
0.035
(8.53)
square
planar
and
determined
8.53). X-ray
average
with
with
by
one
of
bond
the
of
the
plane
rings
[125-J. cyclopalladated
formed
by
the
Of f8rrOCen8
ferrocene
other
were
in
(8.54) was
(N,N-dimethylamino)methylferrocene
(8.55)
active acids and sodium tetrachloroTypical acids used were N-acetyl-L-
acid
and lactic
acid.
in 70% yield
with
The cyclopalladated en enantiomeric
product
excess
of
[126-j, The
002K8,
ferrocene-palladium
COZ4e, COPh
CN,
Acetglferrocene to give the
enil
the complex
complexes
condensed
(a.591 which
with
combined
CuL2. H 2 0, where
/
with
complexes
2
Pd-
CH21DIe2
Cl
0
Fe
*
8.54
were
treated
S-methyldithiocarbazate copper
LH = the anil
of the ferrocenylphosphine
m8 \
8.56)
the corresponding
R1 = H, &i8, R2 = Ph 9 CO Et 2' R = COMe, COPh) [127].
and 8.58; was
(8.54 and
to give
ro- Q Reaction
0
was
was
quite
with olefins under mild conditions 1,2_disubstituted ferrocenes (8.57;
give
with
(8.51).
(8.52
the two isomers
ring
A out
active
obtained
wa-
complex
in methanol.
mandelic
(8.54)
chloride
0
of optically
palladate(II)
sandwich
y-cyclopentadienyl
by treating
valine,
gave isomer
was not
it
conformation
An optically
iron(I1)
dicarbonyl(y-cyclopentadi8nyl)cobalt
The ~ocyclobutadi8ne
anelysis.
with
of dicarbonyl(q-cgclopentadienyl)cobalt
and ferrocenylphenylacetylene Th8
complex
0 ‘3.55
(6.59) (8.60;
ions
to
c-1281. R' = ferrocenyl
/ QP
207
_
I
N
0
PdI
Fe
i
Cl
*
0 8.56
8.57
8.93
8.59
8.60 I
Q
COCH2AuPPh
0
CCCK2HgX
3
Fe
*
Fe
0
0
0
8.61
References
p. 238
,
I“
8.62
or phenyl,
R 2'-- Br) with
Grignard
reagents
gave
the corresponding
comporlnds ~(8.60; R' = Ph, R2 = Me; R' = ferrocenyl, & = D-Fc6Rq) R2 [i29]. organogold
The ferrocene-gold acetylferrocene complexes 8.
Chemistry
method
acylferrocene
with
of the alcohol
in
dilute
and gave
hydrochloric
acid,
without
isolation
the ferrocenylalkene.
For example, l-ferrocenyl-2-methylpropene in 92% yield
gave
this route
Cl34 The cis- and trans-isomers
been
complex
characterized
(8.64).
compounds
or
oxygen
and used
The reactivity
has been
reactions [132]. Treatment of Me)
of ferrocenylalkenes
This involved the reduction of an lithium aluminium hydride and direct treatment
with
isobutyrglferrocene
have
for the synthesis
was reported.
of the alcoholate
via
by treei5ng
.(Ph3PAu)3GfBF -. !?!heferrocene-mercury 4 X = Cl, Br, I) were also prepw8d [130].
(iv) General yield
(8.61) ‘PJasprepared
with
(8.62;
A general high
complex
studied
the tetrahydrofuran
suggested
formed
W< CR
of silica (8.68)
gel gave
whereby
in these and Grignard (8.65; R = H,
in hexane
and the butan-1,4-diol the dimers
ecN Fe
A mechanism were
3
0
8.64
with
the butadiene
dimerization.
0 8.63
Stefen
(8.66; R = H, Me)
by oxidative
for the reaction
Fe
the Pinner,
group
(I-hydroxy-I-a.rylethyl)ferrocenea
gas in the presence
(8.67),
of the nitrile
using
(I-arylvinyl)ferrocenes
derivatives
of the ferrocenylbutadiene (8.63) to form the iron tricarbonyl
produced
(8.69) was via
Fe
Fe
Ft3
Ff3
0 0
8.68
8.67
R
R
Fe
Fe
0 0
8169
Fe
Fi
*
0
0
0
8.70
210
fjypcH2c_cc~ccH20+=&? FE!
*
0
8.71
Fe
6.72
a six-membered molecular
cyclic
oxygen
Cgclizatlon with
hydrogen
basic
medium
The
of
the
addition
chloride product
underwent and was
sodium
hydrogen
chloride,
a typical
addition
aluminium a mixture
of
the
sdphide
water
reaction
were
cis-
and
and
of
the
as
a weakly
(8.72)
butgllithium
2-thienyl) when
the
trans-isomers
to
has
(8.73;
acetylene
chloride used
in
derivatives
ferrocenyl,
of hydrogen
chloride
incorporation
(8.71; R = Br, I)
thiOph8ne
(6.73; ii = Ph, In
by
[133].
molecules
corresponding
of hydrogen
investigated.
R = Ph)
olefin
ferrocenyl-acetylenes or
the
ferrocenylacetglenes been
two
sulphide gave
(8.70) formed
peroxide
into
acetyl
reagents.
The
of
olefin
the
211
i
Q 0
CEC-R
CCl=CHPh
0
Fe
Fe
0
a-73
a.74
(8.74) [135]. Th e cyclopropgl-substituted alcohols (6.75 ; R’ = R2 = R3 = Me; R’ = R2 = R3 = H; R' = H, R2 = R3 = Me; R' = R2 = H, R3 = Ph; R' = Me, R2 = H, R3 = Ph) were prepared from the corresponding ketones. (8.75; R' = R2 = R3 The alcohols = R2 = R, R3 = Ph) were converted to the methyl-ethers =H;R' (8.76;
R = H, Ph) respectively (8.75;
The alcohol corresponding
(6.77)
olefin
chromatography the other
R' = Ne,
on silica
the pyrazoline
derivative the presence
Similar
gel.
ferrocenyl-alcohols
The ferrocenylchalcone form
by methyl
listed (8.79)
(8-80;
ring
protons
in pgrfdine nitro-
in cyano-, containing
was
cyclized
were
gel.
studied
with
with
hydrazine
was acetglated thermal
and potassium (8.81)
trans-diferrocenylcyclopropane Hydrogen-deuterium
reactions
and underwent
carbon
of platinum,
and silica
[136].
R = H) which
(8.60; R = COMe)
alcohol
R2 = H, R3 = Ph) was converted to the and the ring opened product (8.78) by
to
to give
degradation
hydroxide
the in
to the
[137].
exchange
of the substituted
cyclopentadienyl
acetyl-
and benzogl-ferrocene
took place
10% deuterium
oxide.
Carboethoxy-,
formyl-,
and methyl-ferrocene
did not undergo exchange under these and l,l@-dibenzoyl-ferrocene l,l'-diacetyl-
However, conditions. underwent exchange in either pyridine or diglyme [I38]and The reactions of 1,2- and 1,3-diacetylferrocene diformylferrocene
with
aromatic
aldehydes
were
1,2-
investigated.
On
condensation with acetophenone the products from both 1,3-aacetYl_ ferrocen& and 1,2-diformylferrocene were stable but those of 1,2-diecetyiferrocene
Referencesp_ 238
(8.82
and 8.83)
underwent
decomposition
to
8.76
8.75
8.79
8.78
Q-p-Q Fe
*
8.77
Fe
Q-+9 Ft3
Fe
0 8.80
8.81
213
COMe z
Fe
0
COMe
0
8.84
0.02
COCH=CHPh COCH=CHPh COCH=CHPh
I.4
Fe
*
0 0
8.83
8.85
8.1
Scheme
give
derivatives
(Scheme The
8.1)
of 2-acgl-6-hydroxyfulvene
reaction
acglferrocenes
of Grignard
with
optically
with
thioglycoliic
(8.86).
in methanol aqueous
References
P_238
and 8.85)
thiols.
acid
was investigated
Thus
enantiomers
alcohols
[1401.
I-ferrocenylethanol
in the presence was
added
was treated
of trifluoroacetic
a salt which gave
liberated
on treatment optically
to optically
acid acid
active
ephedrine
(-)+-(1-ferrocenylethyl)-
with mercury(II)
active
with
by treatment
(r)-S-(I-ferrocenylethyl)thioglycollic
acid which
acetone
of acetglenic
resolved.into
intermediate
to form
thioglycollic in
were
active
to form
This
reagents
and acglcymantrenes
Ferrocenylalcohols
and acetone
(6.84
[139].
chloride
I-ferrocenylethanol
[lkl].
2x4
7HSCH2C02H
0
Ml3
Q.'
Fe
0 0
Ferrocenylboronic basa hydrolysis acid was
acid was prepared
of ferrocenglboron
converted
in good yield via the The ferrocenylboronic
dibromide.
into hydroxgfarrocene
and
this
was
treated
with
2,3-dihydroppan of this acetal Z-lithiated
to give the ferrocanylacetal (8.87)Lithiation (8.87) with n-butgllithium gave the corresponding ferrocane (8.881, which was used to prepare some
1,2-disubstituted
ferrocenes
("ferrocenyl-aspirin") The propargyl ferrocenrlcarboxylic
including
(8.89)
ester
(8,goj
was obtained
acid with
l,l'-ferrocenedicarboxJrlic
I-carboxg-2-aoetoferrocene
[l42]. proparggl
acid was
by esterification
alcohol,
obtained
the diester
in the
same wag
Co2H
0 13
QFe
Fe
Fe
00
0 0
0.87
of
[143]-
OCOMa
Li-0
0
of
0 0
8.88
8.89
215
C02CH2Cz
C02Me
CH
Fe
0
0
0
0
8.90
8.91
Acetglatlon acetic
COMe
of ferrocenecarboxylic
anhydride-boron
trifluoride
acid methyl
etherate
ester
or acetgl
with
chloride
gave
mainly the heteroannularly substituted derivative (8.91) but some I-carbomethoxy-2-acetylferrocene was also isolated [l/.&]. The ferrocenyl-esters (8.92; R = H, CO,PIe) were prepared by the electrolgsls
of ferrocene
and oxalic
acid
in methanol
on a
platinum electrode. Mono, bis- and tris-(3-methoxycarbonylpropyl)ferrocene were prepared by the electrolysis of ferrocene in the presence of ~Ie02C(CH2)3G02H [145]. The N-ferrocenylmethylpyridini-m to azidomethylferrocene water.
I *-Substituted
similar
reactions
Q
CO,Me
0
Fe
8.92
:
(8.94)
salt
on heating
ferrocenylethylazides
[l46].
t.8.93) was with
sodium
were
converted azide
obtained
in by
216
8.94
8.93
A number
of Schiff
ferrocenecarbaldehyde were
obtained
Typical
were
have
amino
and the compounds
products
DL-SRMe2,
bases
with
been
were
the carboxylic
L-CH2CH2CH2iDIC
by treating
Yields
in the range
used acids
DL-CH2CHIqe2, L-CR2CH2C02H,
L-CH2CH2SMe,
prepared
acids.
as haamatinic
r8.95;
DL-CH2C02H,
(=NH)HH2]
and their
The products
uuderwent
alkylation,
formylation
=
agents. H,
DL-Me,
L-E-CH~.C~H
ethyl
(8.96; R = H, Ph) were [(y-C5R5)Fe(y-CSHbCOCR2C02Et)]
. Ferrocenylpgrazolones ferrocenyldiketones
R
87-9556
esters
.oIi,
147 3. I!
formed from by condensation.
and coupling
with
reagents cl48 3. Formylferrocene was condensed with substituted hydrazines to (8.97; Y = IiH, NMe, NBz, NPh, 0, S) in yields of give hydrazones diazo
51-97s
[Q&9].
Q
CH=NECERCO;IH
0
8.95
8.96
217
f
CH2NHHe2
*
0 8.97
8.98
(Dimethylamino)methylferrocene salt
to form
the corresponding
substituted
was
treated
Reineckate
with
(6.98).
(dimethylamino)methylferrocene
the Reinecke
An
underwent
alkyl the same
reaction
[M]. The thermal
perchlorate subject
decomposition
of ferrocenylmethyldimethylammonium
and ethylenediferricinium
of kinetic
investigation
(Dimethylamino)methglferrocene in near
quantitative
yield
perchlorate
[IS+ was
oxidized
with hydrogen
have
been
the
to the N-oxide
peroxide
[152].
The
aminomethylation
of I,1 r-diethylferrocene and 2,2-bis(l,l'diethylferrocenyl)propane with his(dialkylamino)methanes [(R2R)2CH2 R = Irie,Et, Ru ]in
where
acid was investigated. bis(dimethylamino)methane
acetic
acid
in the presence
3-dimethylaminomethylferrocenes [153]. A series of ferrocenyl polyamines 8.101)
was prepared
diborane were
lymphocytic obtained
by reduction
in tetrahydrofuran.
subjected
to screening
leukemia
with
of phosphoric
With The reaction of l,l *-diethylferrocene gave a mixture of l,l'-diethyl-2and
P-388.
(8.99; m = 3, 4, 6.100
of the precursor
The polyamines for antitumor
(8.99,
8.100
activity
No significant
any of the polyamines
polyamides
and 8.101)
against
antitumor
or their
and with
activity
corresponding
was
pdg-
hyd_~obromides. However, the precursor polyamides [8.102: n = 3, R = H; n = 3, R = (CH2)2COI?H ; n = 2, R = (CH2)3CONR(CH2)2COIiH ] did exhibit
a low but
significant
(Dimethylamino)methylferrocene with
nucleophiles
References p_ 238
to give
antitumor
activity
methiodide
the corresponding
has
[I%].
been
treated
ferrocenylmethyl
218
Q
( CH2 ‘$JH ( CH2),m2
Q
(c~~)ql‘ra(CH~)~~~(~~2)3~2
0
0
Fe
F0
0 0
*
0 8.100
8.99
Fe
8.101
(cH,)~cONH(CH~)~COI~
_Q 0
8.?02
8.103
cH2NtixH2
219
-, Thus
compounds. hydrazine been
of nitrogen
prepared
the sodium product
in 80%
(6.103)
A number have
rezctiion
with
hydraAm
yield
ga7e
ferrccsnylmethyl-
[155].
heterocgcles
by treatment
with
ferrocenyl
substituents
of ferrocenylmethylchloride with A typical heterocyclic anion.
salt of the appropriate
was the ferrocenylmethylaminotetrazole
(8.104)
[I_%].
Fe
0 0
8.104
9.
BIFERROCERES, Ligand
FERROGEWOPRANES
exchange
(L = benzene,
reactions
mesitylene,
the dications
biferrocenyl
(9.2) were
-Q--Q 0
'Fe
9.1
Referencesp.238
L
and tetralin) were effected In the presence 'of one c'hloride. were
formed
isolated
and with
[157]. 2f
+
0
and arenes
naphthalene
in the presence of aluminium mole of arene the cations (9.1) arene
AND ANiK%_&IED FERROCERES
between
-@q-
Fe
Fe
Fe
L
L
L
9.2
two moles
of
220
Neuse
and co-workers
dilithioferrocene coupling
experiments
-taken to exclude
pure (9.3)
were used
formation
of cobalt
from
of I,I*-
chloride.
dioxide.
and the degree that step,
the coupled
of
of polymerization
the reaction followed
entity
were
A series
of di- or multi-nuclear
addition
In the
and precautions
and carbon
was obtained
from an oxidative
I
Fe
oxygen
the coupling
of cobalt(I1)
It was proposed
relatively high. via the intermediate
wes
elimination
studied
reagents
molecular
polyferrocenglenes
complexes
have
in the presence
proceeded cobalt
by the reductive
[ISS].
IT
Fe
Fe
9.3
Intermolecular in t'ne presence
coupling
'hydride and tributglam&e ferrocenyl)ethylene Catalytic
chloride,
mixture
to give
lithium
hydrogenation
of the unsaturated (9.6).
by the reductive
1,2-bis(l'-formyl(9.5)_
derivative
The ferrocenophane
coupling
occurred
aluminium
(9.4) and the [2,2]ferrocenophane
the [2,2]ferrocenophane prepared
of I,1 *-diformylfsrrocene
of a titanium(IV)
(9.5) gave
(9.6) >ras also
of 1,l *-di(hydroqmethyl)ferrocene
[?59]* T%e synthesis and
of [Z]orthocyclo[2](?,2)ferrocenophane
[2,2](1,2)ferrocenophane
trimethylammonium phosphorane and then
salt
(9.11) has
been
(9.7; X = N+Ke31-)
(9.7; X = PiPh31-)
to the
to the diferrocenylethane
was
(9.10)
reported.
The
converted
via
diferrocenylethylene
(9.9).
Cyclization
the (9.8)
and
subsequent reduction gave the ferrocenophane (9.11) as a mixture T'ne orthocycloof two isomers (9.11a and 9,llb) in the ratio 3:l. ferrocenophane stereochemistry
(9.10) was
synthesised
of toe lerrocenophanes
by a similar
route-
(9.10 and 9.11)
was
The
221
QcH=cHQ OHC
CHO
@CH=CH.@)
9.5
9.4
Fe
Fe
@cH2cH2--@ 9.6
compared chair,
with
boat
of [2,2]orthocgclophane
and twist-boat
conformations chair
that
conformations.
for the trans-ferrocenophane
(q.731,
(9.~6).
exo-erdo (9.141, -endo-exo -it was considered that the most
(9.12) wnich
may
adopt
The four possible (9.'l?a) are -exo-exo boat (9.15) and -endo-endo favourable
conformer
was
Similar arguments were developed the -exo-exo chair.form (9.13). for the cis-ferrocenophane (9.11b) and for the orthocgcloferrocenophane
(9.10) [160]. The synthesis of some trimetii~lene bridged ferrocenes has Previous reports that the tribridged compound reinvestigated. (9-17) could were
References
shopm
p_ 233
be converted
to be incorrect
to the tetrabridged and
the last
ferrocene
compound
(9J8)
been
(9.16) has
been
Fe
Fe
Fe
:@
6 0
0 9.8
9.7
9.10
9.9
9.11a
- fzmns
9.11b
-
cis
223
x
exo-endo
- 9.14
I
11
_I A--kFeA endo-exo
6X0-8X0 rsfomulated to prepare obtained
endo-endo
- 9.13 as the
homoannular
a'pent=bridged
bridged
ferrocene
potentials
for ferrocenes groups
The conformations
showed
bridged
and configurations
(9.19).
- 9.16
Attempts
the product
bridges.
with
a correlation
ferrocene
were unsuccessful.,
(9.20) -contained homoannular
methylene
- 9.15
one, with
The electrode two and three tri-
the engle
of several
of ring-tilt.
bridged
ferrocenes
were
discussed and related to previously reported Noessbauer results structures of three multibrieed [161]_ Th e crystal end molecular
ferrocenes
(9.19, 9.20 .znd 9.21) hsve been co_nfirmed by X-rag One of t'nese structures (9.19) had been claimed crystallography. previously by kchl~gl and Peterlik [162)as the tetrabridged ferrocene
Refer&es
p. 238
(9.18)
[163,
164,
1651.
224
9.17
9.19
9.21
9.18
9-20
225 1 H and.13 C MR structure
and coupling and were The
spectroscopy
have-been
[3] ferrocenophanes
of the
constants
in agreement
for with
the bridge
in borax
approximately Photo-oxidation (9.26) and
240
occurred
acids
(9.24) and
in the presence
to give
(9.25) were
with
light
of nitrous
the corresponding
9.24
I
Refere.ncesp.238
9-26
of oxide.
zwitterions
(CH213C02H
9.25
[166].
structures
[167].
9.23
the shifts
were obtained
atoms
proposed
of pH 9 arid irradiated
run wavelength
(9.27)
9.22
buffer
investigate ChemLcal
9.23).
hytiogen
the previously
4-([3]ferrocenophanyIngl)butanoic
dissolved
used.to
.(9.22 and
9-27
226 The
dihgdrodicgclopentanaphthalene
the corresponding binuclear last
converted
to
and then to the The binuclear chloride.
ferrocene (9.30
c5?3 00
\
(9.28) was
with n-butyllithium
(9.29) with iron In the and 9.31) were formed in the same way. proportion of the trinuclek ferrocene (9.32) case a small [168]. obtained from the trianion and iron(I1) chloride
ferrocenes was
dianion
/
Fe
Fe
Fe
0 @ 9.29
9.31
00° 9.30
Fe
Fe
0
9.32
227
n
10.
FERROCENE-CONTAINING The preparation
has been
discussed
POLYN3RS
of ferrocene by-Korshak
l,l'-ferrocenedicarboxylic
monomers
and their
and Sosinb@].
polymerization
Ethylene
acid-terephthalic
glycol-
acid copolymer
gave
fibres with good photostability and oxidative thermostability. The crystallinity of these fibres on orientational elongation and the degree
higher
of orientation
dimethyl
ferrocene, modified
terephthalate
polg(ethylene
was
lower
than
fibres [170]. and polgcondensation
polg(ethylene terephthalate) me transesterification
and ethylene
terephthalate)
that
was
of
of I,l'-diacetyl-
glgcol
containing
gave
a
l,l*-diacetyl-
The reaction involved the intermediate formation ferrocene groups. of dioxolane derivatives of the substituted ferrocene and the subsequent formed
cleavage
fibres
light
of these
which
and under
poly'(ethylsne
showed
oxidative
Fibre-forming of dimethyl proportion
C
compositions
or break
when
isoprene,
obtained glgcol
with
by the copolymerization
together
did not
elongation
and
terephthalate),
suffer
after
with
a small
or l,lt-dibutyrglferrocene.
the poly(ethylene
UV irradiation
chemically
1-12s
Fibres
a reduction
was homopolymerized
butadiene or
Various
and
obtained
in mechanical for ten days at
in the presence accompanied
containing
polymers
chloride)
of aluminium
chloride.
were
in
the
obtained
treated
Soluble
composition
unsaturated the Vicat
of
the
polyesters softening
Referen-p.233
of
was also
with
polymers
reactions,
ferrocene containing substitution
[174].
A fire-resistant unsaturated resin has been 1,2-polybutadiene with ferrocene in the presence Good fire resistance with an amine hardener
presence
such aschlorinated
were
and in most
by dehydrohalogenation
[175].
with
[173].
metal
and polg(viny1
up to 62% ferrocene
and copolymerized
l,&dibromohexane
lithium
halogen
polyethylenes
me
by
[l-72].
n-butyllithium
resin
compared
the transesterlfication
copolymer
Vinylferrocene
was
were
ethylene
catalyzed
into
the brown
strength
conditions
polymer
to degradation
['l71].
terephthalate,
incorporated
40°
stability
of 1,l I-diacetylferrocene
The metallocene from
thermal
terephthalate)
The modified
intermediates.
improved
formed by heating of benzoyl peroxide
by curing an epoxy in the presence of ferrocene [I76-j. oligoester used to form ferrocene-containing
has been
point,
shown
the Brine11
achieved
theoretically hardness
to determine
and the Stress
228
Causing
failure
shotred high They
were
during
bending
reactivity
proposed
of the polyesters.
were
and
as binders
amenable
to hot
for glass
of vinylferrocene composition
was
with
was based
vinylferrocene
obtained
suitable and AIBN
2 parts
or 1,2-polg-
A typical
50 parts, which
plastics
copolymerization
monomers.
on 1,2-polybutadiene
30 parts
polyester
by the radical
organic
polymers
fibre-reinforced
and electrical insulators [177]. A fire- and heat-resistant unsaturated 'outadiene composition
These
or cold curing.
stgrene
were
heated
five hours
at 100° C to form the cured resin, The resin for 250 hours at 15Oo C without any change in electrical mechanical properties and without the evolution of smoke
50 parts,
for
was heated and OF
t0X.h
f’umes
[178]. Ferrocenylacetglene of THF' and ethanol using
has been polymerized at 60° C in a mixture bis(triphenylphosphie)nickel(II) halide
The polymer was separated by precipitation complexes as catalyst. cm-l with ether and had an electrical conductivity of IO -IQ-1 [179]. Polg(acrgloylferrocene) fractions
and the thermal
temperature
at which
was measured eratures values
was
divided
stability
10% weight
loss
for each fraction.
The
of 310° C and
of 250°
350° C while
into
soluble
of each was
investigated. The in air and in helium
occurred soluble
fraction
the insoluble
C and 320° C respectively.
The
thd stability
of poly(methy1
acryloylferrocene
Acryloylferrocene methacrglate
was
and styrene
as the initiator,
methacrglate) [1803. copolymerized
in benzene
The last
using
thermal
two copolymers
was with
gave
fraction
of polystyrene, poly(acrylonitrile) and poly(viny1 enhanced by the incorporation of acryloylferrocene incorporating
and insoluble
stability
acetate) residues
decreased vinyl
tempgave was but
by
acetate,
methyl
azo-bis-isobutyronitrile were
obtained
in 80%
yield or better and while some homopolymerization of the organic monomers was detected, acryloylferrocene did not form a homopolymer under these conditions. 'The ratios of acryloylferrocene units to organic
units
were
1, 0.59
and 1.37
for vinyl
acetate,
methyl
methacrglate and styrene respectively [I~I]. Ferrocenylmethyl methacrylate underwent anionic polymerization in a high vacuum system using lithium aluminium hydride-tetramethylTne living polymers obtained combined ethylenediamine as catalyst. with
methyl
methacrglate
"rile and acrylonlti
to give ferrocenglmethyl
229
methacrylate-methyl
methacrglate
acrylonitrile
copolymers
of
SkgreEe
since
block
to
the living
the polymerization methyl
polymer
anions
the polyxner
were
to living
Interfacial ferrocene
was
obtained
copolymer by adding
[182]. has been used
condensation
a block
the addition copolymer
as nucleophiles
The block
polystyrene
methacrylate-
However,
dfd not give
too weak
of stgrene.
methacrylate-styrene
monomer
and ferrocenylmethyl respectively,
to initiate
ferrocenylthe ferrocenyl
to prepare
dioxime-di(T-cyclopentadLenyl)titani.um
l,l'-diacetyl-
dichloride
The importance of stirring copolymer in near o_uantitative yield. time, stirring rate, monomer ratio and solvent on the reaction was
evaluated
['l83].
Vinylferrocene with
radical
azo-bis-isobutyronitrile
ization with
underwent
was linear
ti-me-
tow20$
Aggregation
precipitate
ccnversion The ZSR
snd then
of paramagnetic
species
poly(g-vinylbenzophenone) occurred chain
light.
and recombination
resulted
in intra-
of the ferrocene
group
irradiated
with
increases break
and decreases
was dependent dose
increasing
and then
were
decreases
the quantum
with
ferrocene
doses
of x-rays
in tensile
in solubility,
on the proportions
irradiated
located
and inter-molecular
chemical reactions [ISS]. Copolymers of ethylene
a
confirmed
and
copolymer
of the benzoquinone
of t‘ne radicals
reduced
caused
of the polymer
block
in iso-propsnol
Photoreduction
progressively
conversion
[184].
p-Vinylbenzophenone-vinylferrocene ultraviolet
of polymer-
decreased
at high
spectra
in benzene
The rate
as initiator.
of the polymer
to be formed.
the presence
polymerization
The
in the polymer The presence
reactions. yields
with
groups
,
in the photo-
a.2d v?.nylferrocene were and showed sequential
strength
a-n-delongation
detailed
form
of comonomers
and
at
of the changes
the radiation
[136]. The
thermochemical
copolymers
with
polg(ferrocenylmethy1 styrene
of polyvinylferrocene,
its
and methyl
methyl acrylate and methyl methacrylate; methacrylate) and its block copolymers with
methacrylate
were measured
over
the temperature
thermogravimetry and an automated Polyvinylferrocsne was found to undergo torsional braid technique. irreversible changes in the temperature range 220° to 3oo" so that
range
-180~
properties
styrene,
to 250° using
the glass transition temperature (Tg) was not obtainable directly ^_ but extrapolated from the Tg values of its random copolymers-
References p. 238
230 a low value
was
obtained
by this method
value of Tg for poly(ferrocenylmethy1 that obtained by direct determination. by m-bis&-PhenoxyphenoxyIbenzene concentrations polystyrene
with
of plasticizer
Polgferrocene method
several
film
films
have been
th$9snesses
11.
was plasticized
in Tg at low
than
in plasticized
by the plasma
small
Results
arose
of plasma-polymerized
from
for
the
ferrocene
constant
investigated. for aluminium-polyferrocene-aluminium tans, showed
polymer-
measured.
that conduction
The dielectric
increases
E
and the sandwich
in the temperature
range
[189-j.
APPLICATIONS
OF FRRROCETJE
(i) Ferrocene
catalysts
The incorporation density
gave
use when
quality
into
low
a photodegradable
formed
the soil temperature
and nutritional
and photosensitizers
of 0.0_5$ oc-hydroxyethylferrocene
polyethylene
agricultural crops
polymer
to
[I883.
current
.tb.in-films were
30-400’
formed
conduction
suggested
Tfiedielectric properties factor
This
was equal
a decrease
that was greater
and the electrical
space-charge-limited
structures,
the extrapolated
[187],
ization
loss
but
metbacrylate)
into
was
material suitable for When used on potato thin film.
increased
of the crop
by 2.5O
improved
C and the yield
[?90].
The photodegradation of polyethylene was accelerated by the introduction of a small proportion of acetoxgferrocene or d-hgdroxgethylferrocene,2,4-dinitrosoresorcinol into
the polymer
[191].
Photodegradation up to three-fold were
added
of coloured
when
of patents
groups
on polymers
was
together
with
having
O,Ol-20
was
enhanced
and iron(ii1)
by oxide
b92]. taken
deriva-tives in positive-warking were based
polyethylene
1-hydroxyethylferrocene
as photosensitizers
A series
and benzophenone
out on the use
radiation
of ferrocene
The resists
resists.
halocarbonyl
and/or
wt f of a ferrocene
carboxylic derivative
acid [ll.l:
R' = R2 = OH, CH20H, (CH2)20H, (CH2)30H, (CH2)40H]as a sensitizer Similarly a series of other ferrocene derivatives were [7931. The addition of the used as sensitizers in a range of polpers. ferrofene
derivatives
of the resists
greatly
increased
[?94, 195, 196, 1971.
the electron
beam
sensitivity
231
Q
R'
0
Fe
0
0
R2
11.1
Radiation
resist
compositions
were
prepared
that
contained
O-1-30 Wt $ of a metallocene (11.1; R1 = R2 = R, OR, ~_hy&oxyalkyl, CHO, C02H, alkoxgcar"oonyl, halogen; K = Fe, Ni, co, cr, r~l, RU). The resists integrated
were
circuits
A light from
that
useful
composition
or a ferrocene
and an analytical
with
reagent
image was
this wasfixed
an image
composition
derivative for
iron
an organic
obtained
2 parts
and polystyrene and acetone.
on exposure Thus, iodoform
and gave
a clear
blue
10 parts
were
The solution image
after
colour
by mixing halogen
by mking
dye, ferrocene
compound
was
4.2
dissolved coated
exposure
iodoform,
and a binder.
of the composition 4 parts, 3,3-bis-
(dimethylaminophenyl)_6-dimethglammophthalide toluene
in
[199].
obtained
by heating.
different
was prepsred
wFth
compositions were Photoimaging the leuco form of an 2cid sensitive A coloured
and
[198].
sensitive
of the unmodified
ferrocene
of semiconductors
for the fabrication
parts,
and
ferrocene
in a mixture
of
on a polyester
and
fixing
base
[200].
Phototiaglng For example,
compositions containing ferrocene were prepared. 3,3-bis-(L+'-dimethylaminophenyl)-6ferrocene, trichloroacetamide
dimethylaminophthalide, dissolved
in a mLxture
polyester
film
References
which
p. 238
me
support.
_at 110~ to give clear Ferrocene formed bromide
of toluene
was
film
and polystyrene
blue images (2011. a charge-transfer complex
active
were
and acetone and coated on a was imagewise exposed and fixed
photochemkally
with
and was used
carbon
tetra-
to form
232 photographic was
images.
implicated
The formation
in the production
A photosensitive anodized
aluminium
composition
foil with
of ferricinium
of images
was prepsred
a mixture
tetrabromoferrate
[202]. by whirl
of a halogen
coating
an
containing
and a plasticizer in dic‘nloropolymer, carboxymethylthioferrocene The plate was exposed imagewise and then developed with ethane. a solution of Teepol in aqueous ethanolic sodium hydroxide to give a plate
'with improved
ink receptivity
Dimethylterephthalate in the presence
and ethylene
photoinduced
suspension
tetrachloride
as the initiator the water
were
ion was
the ferricinium
ion to ferrocene
of polymerization the addition
rate.
It was of the
n-Type a cell
layer
silicon
together
irradiation
of sodium
in the lauryl
of polymerization bromide
was
decreased
affected
as a stable
to electricity.
in less
than
(ii) Ferrocene The use
was
oxidized
approximately
silicon was
The
the
ion
by the
photoanode
in
other
of ferrocene
and fillers.
100s
ion at a
efficiency.
Prolonged cell gave a constant
of the ferrocene-ferriciniu which
It
dropped
by more
couple than
90%
[206-j.
stabilizers
it was
couple.
to the ferricinium
in a one-compartment
obtained
ten minutes
investigated
when
the ferricinium-ferrocene
In the absence
Photocurrent
binders
with
with
of the
a lower
catalyst
of light
that
of ihe ferricinium
layer
[205]. sho1.m to behave
t'nat ferrocene
photoanode
was
the transfer
to the water
was
an increase
The addition the rate
showed
acid reduced
in the cell were a platinum cathode and an electrolyte of au ethanol solution of tetra(n-butyl)ammonium
photocurrent.
againg
that
emulsifier
silicon
perchlorate was found
was
of
arid carbon
In the suspension which
of ascorbic
and there
increased
for the conversion
components consisting
Addition
blue
of cetgltrimethylsmmonium
suggested
the monomer
became
of the FWL.
as an emulsifier
whilst
charge
formed.
polymerizations
of ferrocene
investigated.
layer
the ferricinium
from
and emulsion
(NiW) in the presence
photopolymerization
sulphate
were POlyIWPiZad
to give poly(ethylene
[2O4].
methylmethacrylate
rate
glycol
of ?,I'-diacetglferrocene
terephthaiate) The
[203].
and improvers derivatives as inhibitors of Polyethylene Ferrocene behaved as a dehydrogenation
[207].
added These
to friction materials
materials were used
containing
organic
in the formulation
of raiI=Y prevent
brde
shoes and the presence fade [208].
brske
k storage-stable on cadmium benzogl
surfaces
peroxide
been used
has
anaerobic
composition
was prepared
and ferrocene
from
(11.3)
The 2-ferrocenylbenzoquinoine and polyamide
helped
capable
to
of hardening
oligocarbonate
[209].
acrglates,
The diacetglferrocene
as a dye for polyjethylene
for polyester
Q 0
of ferrocene
terephthslate)
has
materials
been
(11.2)
r2101.
claimed
as a dye
[211].
COMe
0
Fe
0
CONe Fe
*
0
11.2
11.3
(iii) Ferrocene Ferrocene amperometric slags.
in analysis in ethanol
titration
acid was added
The kinetics and vanadium(IV) that
of vanadium
could
by ferrocene
acid and acetic could
titration with Solomatin mination Iron(III),
acid.
be determined
was It was
media
The found
in steels
out
that
with
and rhenium(VII!
determination titration
vanadium(V)
alloys
were
of
of sulphuric and vanadium(IV)
by amperometric
a method using
[212).
investigated
in a mixture
devised
case and
vanadium(V)
were
of each other
and
in metallurgical
of vanadium
amperometric
carried
the
in each
for the titrimetric
ferrocene [213]. and co-workers have
molybdenum(VI)
Reference.sp.238
of ferrocene
in the presence
of molybdenum
was used
aqueous-organic
be selected.
for
and iron(II1)
in the determination
cond9tions
vanadium(V)
as a reagent
acid medium
of the reactions in acid
the opt5m~~11
used
of vanadium(IV)
An acetic-sulphuric
phosphoric
SO
has been
for
the deter-
ferrocene
determined
[274 ]-
inairec*lY
by reaction
with
ferrocene
to give
the ferricinium
ion
and the concentration of this latter ion was estimated spectrophotometrically at 675 nm. Molybdenum(VI) and copper(II1 behaved as interfering ions in this estimation whilst manganese(II), iron(X), metals
cobalt,
did not
nickel,
interfere
The amperometric ferroeene
in acetic
The best
medium
for
Under
leadfIr), but
these
nitrate
zinc(II),
of the conditions by ferrocene
The optimum
conditions
mixture.
interfere
but
chrom;-Um(VI)
iron(III),
with
investigation.
A ferrocene
6M hydrochloric acetic redox
acid.
dimethyl acid
couples
A series cyanide
been
was
cations
of ferrocenes
of Cu2+/Cu+ electrodes.
tetrafluoroborate The properties
found
and immersed
silylferrocene Cyclic
voltmetrg
electrolyte
was
difference
germanium
in an iso-octane
lOrg
aqueous
of hydrochloric Se/20 mL any
[218]. by coulometric
reaox were
and the
acid,
system
oxidized
titration,
in methyl
of 20-50 mV between
The ferrocenes
with
and the ferricinlum/ acetic
was
was determined
[2.19], of n-type
(11.4)
limit
as an auxiliary
order
at a range
examined
was used
in SO,% aqueous
to be second
in aqueous
of
of a kinetic
of 0.025M
propanol
surface-bound ferrocene residues germanium crystal was pretreated acid
acid-
and
titration
the subject
concentration
The detection
ana a potential
indicator
mercury
for the emperometric
have
and aqueous
by metal
acetic
did not
[217].
determined
were
concentrations.
by the use
in a 1 :I
silver,
ion
did
solutions.
metals
of the selenium(N)/selenium(O)
sulphoxide
interference
acid
and alkali
acid as the supporting The reaction
potentials
ferrocene
earth
tsllurium(IV),
for the amperometric
in aqueous-organic
~3% sulphuric
necessary ferrocene
acid containing
ion and phosphate
required
with
investigated-
and silver(I)
thallium(III),
did interfere
The conditions selenium(IV)
were
The alkaline
was
thallium(I),
iron
copper(
titration water
earth
and mercury(II)
P acetic $5'0"
was
conditions
interfere [216). A st;udy was made of lead(IV)
and alkaline
acid mixtures
the titrations
selenium(IV),
interfere
of mercury(I)
acid-perchloric
acid.
alkali
zinc,
[215].
titration
3N perchloric did not
caomium,
platinum
by copper
sexniconducCors
with
have been investigated. The by anodization in 6~ sulphuric solution
of either
tricfiloro-
or I,1 '-bis(dichlorosilyl)ferrocene
of the derivatized
surface
in ethanol
(11.5). or
235
0
Q
SiG13
0
Si(OEt)3
0
Fe
Fe
is 0
0
?1.4
11.5
acetonitrile
11.6
of tetrebutyk3mmonium
SohtiOns
si(ost)j
0
perchlorate
confirmed
that the r'errocene groups were firmly bound to the surikce. the electrode caused the anodic current peak to Ilhminztion of be moved by up to -200 mV to more negative values Mhich was consistent with the anticipated photoeffects for an n-tgoe semiconductor, Comparisons between the derivatized electrode and a naked n-type germanium photoelectrode in electrolytes containing ferrocene indicated that the interface energetics and kinetics prere unaffected by derivatisation [220]. Platinum and gold electrode surfaces have also been derivatized with the silglferrocenes (17,k, 11.5 and 11.6). The ferrocene groups appeared to be bound to the metal by Si--G+I linkages where $1 = Pt, Au. me derivatized electrodes gave persfsteni; cyclic voltanznetric ferrocene
one-electron surface
was
Several acfd,
waves
at a potential
expected
derivative anu the parameters system. founu
Greater
in each
case
ferrocenecarboxylic
I,?'-ferrocenedicarboxylic
(71.7 and 11.8) r-leretimobilized
for an electroactive
accorded
than monolayer
with
coverage
a reversible, of the
[2273, acids acFu on
including
ferrocenylcarboxylic
and the carboxylic
a plat;lnum oxide
acids
electrode
residue. !Fhemode of binding is idealized for fesrocenglcarboxylic acid in the Iu;lide(11.9). X-ray photoelectron spectra were obtained and were used to support the structural assignments of the bound metal3_ocenes. Cyclic vo3.tammetry was used to investigate the electrochemical properties of the modified electrodes and the surface
tbrougb
Referencesp.2383
a 3-(2-eminoethylzmino)propgltPimetho~s~l~e
236
Fe
Fe
11.7
Q
11.8
*
~oEH(~H~)~~(CH~)~S~-O~
0
2 :
11.9
second-order case
of
ferricinium
ferrocenglcarboxylic
Darameters
were
immobilized
(iv)
Combustion
the added
pollutants,
to
acid
and
i:er& described.
tine non-ideal
ferricinium
over
with
monolayers
protection
The treatment
mineral
product
in
surface
stability
the
activity
was
enDanced
for
[222].
against of
ferrocenes,
oils,
non-basic
of polgethanolamine
It gave
gasoline.
substituted
kinetics
control mixed
car_densation
and was
and
smaller
multilayers
Perrocene
[223].
decay
coal
a reduction corrosion
with
and
iron
hydrogen,
and
in
and
ester
the
fatty
emission
carburettor
compounds, nitrogen
solvents of
cleansing
such or
acids
as
carbon
ferrocene
237 monoxide such
at
250°
increased
as
pyrites,
and
methods. _ -
Clean
coal
(v)
Biochemical
the
urine
and
B
and
Rats were from
oral
(approximately
only
sulphate
shown
of
in
of
the
small
in
its
The
prepwed was
absence
md
tfielr.
in
of
impurities
by
magnetic
this
method
(UDPGA)
(11.10)
was
A
which
the
Metabolite
in
A,
thought B was
metabolism
was
related
a
shown
to
ferrocene and
in vitro
to
the
observed
if
incubations
[225].
compounds
in mice
to be
cofactor
formed
added
not
activity
of
NADPH
was
was and
and
dose)
ticrosomes,
glucuronide
antineoplastic
oil
metabolites
metabolite the
In vitro,
sesame
isolated.
end
hydroxyferrocene
ferrocenyl-amide
by
Two
quantities,
uridine-St-diphosphoglucuronate but,
ferrocene
were
liver
Ferrocengl
oxygen.
yield
administered
intact
viable
separated
98%
collected.
of hydroxyferrocene
require
to be in
was
glucuronide.
to
moleculer
26%
susceptibility
applications
doses
remained
present
ester
ferrocenyl
was
biological
animals
which
these
obtained
these
nucleus
be
enabled was
given
ferrocene was
t&magnetic
Were
against
sarcoma
[226].
studied
Fe
0 0
11.10
A number synergists the
for
deposit
ferrocene to
Musca
ineffective
of
kn9"
left and
substituted
ferrocenes
insecticides
after
and
evaporating
were
shown
of
[ZZ?].
whereas
the
components
as
example,
1% c(-propionyl-
2-isopropyloxyphenyl-N-methylcarbonate
domestica
behave
For
acaricides.
a mixture
to
themselves
was were
lethal
238
Ferrocenylcholine were
shown
to inhibit
the enzyme
horse
Ferrocene agricultural acetic
acid
serum
derivatives
2
Aced, Sci., 295 N. s. Kochetkova
9
after
as iron-containing
dilution
and mixing
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A. N. Nesmeyanov, E, N. Stakhaeva
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was used
W. J. Pannekoek
and R. B. Materikova, IO
claimed
Ferrocene was treated with trimethylacid at 100° C to form trimethylacetgl-
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