Bimetallic π-conjugated complexes modulated by a carbonyl spacer: Synthesis of arenetricarbonylchromium-ferrocene derivatives

Article abstract of DOI:10.1016/S0022-328X(00)00833-0

Heterobimetallic complexes modulated by a carbonyl spacer have been prepared in the case of arenetricarbonylchromium and ferrocene derivatives via Claisen-Schmidt condensations.

Full text of DOI:10.1016/S0022-328X(00)00833-0

Journal of Organometallic Chemistry 624 (2001) 124–130
www.elsevier.nl/locate/jorganchem
Bimetallic p-conjugated complexes modulated by a carbonyl
spacer: synthesis of arenetricarbonylchromium–ferrocene
derivatives
Damien Prim, Audrey Auffrant, Zoi F. Plyta, Jean-Philippe Tranchier,
Franc¸oise Rose-Munch *, Eric Rose
Laboratoire de Synthe`se Organique et Organome´tallique, UMR CNRS 7611, Uni6ersite´ Pierre et Marie Curie, Tour 44-1er e´tage,
4 Place Jussieu, 75252 Paris Cedex 05, France
Received 2 October 2000; accepted 20 October 2000
Dedicated to Professor Jean Normant on the occasion of his 65th birthday
Abstract
Heterobimetallic complexes modulated by a carbonyl spacer have been prepared in the case of arenetricarbonylchromium and
ferrocene derivatives via Claisen–Schmidt condensations. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Arenetricarbonylchromium complexes; Carbonyl spacer; NLO; Claisen–Schmidt; Ferrocene
dithienylketone structure was proposed through the
following zwitterion-like species (Scheme 1).
1. Introduction
In the past decade, highly active chromophores with
large quadratic hyperpolarisability i have attracted
much attention because of their interesting non linear
optical (NLO) response. Their particular properties
have usually been observed when connecting an organic
electron donor to an organic electron acceptor via a
p-conjugated backbone [1].
However, in a recent publication Persoons and co-
workers [2] pointed out the crucial role played by non
conventional keto spaced chromophores based on
dithienyl derivatives, in tuning the charge transfer along
the push–pull conjugated system. Indeed, these authors
suggested that the carbonyl spacer did not interrupt the
charge delocalisation between the terminal donor and
acceptor groups leading to high NLO efficiencies.
Moreover, conjugation between the electron withdraw-
ing and the electron donating tails of the substituted
They observed two different stages, the first one for
an external electric field below 6×107 V cm−1, the
charge delocalisation occurred from the donor to the
carbonyl, the spacer playing the role of the main accep-
tor group. Beyond 6×107 V cm−1 the spacer was
saturated and transmitted electrons from the donor to
the acceptor. Thus increasing the external field allowed
charge redistribution in the molecule leading to polar
species. As there is a large difference of dipolar moment
Dv between the ground and the excited states, which
are separated by a large enough band gap energy, such
organic molecules exhibit high second-order polarisabil-
ity i.
According to these results and knowing that
organometallic complexes have been shown to exhibit
good NLO properties [3], we were tempted to investi-
gate the behavior of bimetallic complexes containing
such keto-spacers. We report here the preparation of
new Cr–Fe dinuclear complexes where the chromium
fragment is linked to the ferrocene entity by conjugated
carbonyl spacers (Fig. 1).
* Corresponding author. Tel.: +33-44-276235; fax: +33-44-
277089.
E-mail address: rose@ccr.jussieu.fr (F. Rose-Munch).
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(00)00833-

D. Prim et al. / Journal of Organometallic Chemistry 624 (2001) 124–130
125
Scheme 1. Schematic representation of the evolution of the molecule upon application of an external electric field.
2. Results and discussion
We extended this strategy to the building of a more
rigid keto-spaced backbone and we performed the same
kind of condensation with a cyclic ketone (Scheme 5).
Condensation of cyclohexanone carbanion with fer-
rocene carboxaldehyde 3 afforded 6 in 60% yield a
further lithiation–condensation sequence using LDA
and benzaldehydetricarbonylchromium 2 gave the ex-
pected complex 7 in 45% yield.
We also tried to extend the spacer’s length with a
thienyl unit known for its intrinsic properties in NLO
materials [9]. Indeed, since the ground state aromaticity
of thiophene is lower than that of benzene, much
attention has been paid to chromophores containing
this unit. Unfortunately reaction of ferrocenyl deriva-
tive 5 with aldehyde 8 did not afford complex 9
(Scheme 6). According to NMR spectra, the crude
mixture showed the presence of polycondensation prod-
ucts that we were unable to separate and to analyze,
due to their high instability.
We generalized this method to the synthesis of other
bimetallic complexes with various spacer’s lengths using
acetylferrocene carbanion.
As mentioned above, LDA was used as base to
afford deprotonated acetyl ferrocene species. Subse-
quent reaction with benzaldehydetricarbonyl chromium
2 gave 60% yield of complex 11.
Complex 12 was obtained in 21% yield under similar
conditions using 5-(h6-thiophene-2-carboxaldehyde)-
benzenetricarbonylchromium 8.
One of the most useful way to obtain keto spacers
with concomitant creation of carbon–carbon bonds is
to use the efficient addition of carbanions to aldehydes
or ketones. Few reports deal with Claisen type reac-
tions involving an organometallic carbanion and alde-
hydes or ketones. For example, complexed benzylic
carbanions obtained from allyl or alkylbenzenetricar-
bonylchromium derivatives [4] in basic medium lead to
the formation of ketones after addition of aldehydes
and subsequent oxidation [5] (Scheme 2).
On the other hand, it has been shown that condensa-
tion of a-alkylmethylketone anions to benzaldehydetri-
carbonylchromium complex afforded the corresponding
ketol derivative at low temperature. Deshydratation of
the ketol gave rise to chalcone structures at higher
temperatures for prolonged reaction times [6] (Scheme
3).
To the best of our knowledge, no Claisen type reac-
tion has been described involving two organometallic
reactants. This strategy was chosen for the preparation
of new bimetallic complexes.
As depicted in Scheme 4, complex 1 was obtained
through two successive so called Claisen–Schmidt con-
densations [7] starting either from benzaldehydetricar-
bonylchromium
2 [8] (pathway a) or ferrocene
carboxaldehyde 3 (pathway b).
Conjugated ketone 4 was first prepared using acetone
and benzaldehydetricarbonylchromium in the presence
of aqueous potassium hydroxide. Carefull deprotona-
tion using LDA and subsequent addition of ferrocene
carboxaldehyde 3 directly afforded complex 1 (Scheme
4, path a). As a result of the well-known stabilization
effect of the Cr(CO)3 entity, the reactivity of the carb-
anion of 4 is weakened, giving consequently a poor 4%
yield together with several unidentified polycondensa-
tion products. Complex 5 could be obtained from fer-
rocene carboxaldehyde 3 and acetone in the presence of
aqueous potassium hydroxide. In contrast, treatment of
5 with LDA gave a more reactive carbanion, destabi-
lized by the donor effect of ferrocene. Addition to
benzaldehyde tricarbonylchromium 2, allowed the
preparation of complex 1 in an overall 60% yield.
Fig. 1. Design of new bimetallic Cr–Fe complexes.
1
The H-NMR spectrum of 1 showed a characteristic
vicinal coupling constant of 15 Hz for H7 and H8
protons in good agreement with a trans configurated
double bond created by the Claisen–Schmidt
condensation.
Scheme 2. Condensation of allyl or alkylCr(CO)3 carbanion.

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D. Prim et al. / Journal of Organometallic Chemistry 624 (2001) 124–130
Scheme 3. Preparation of chalcone–Cr(CO)3 derivatives.
Scheme 4. Preparation of conjugated areneCr(CO)3–ferrocene derivatives.
Scheme 5. Preparation of areneCr(CO)3–ferrocene derivatives.
Scheme 6. Condensation of ferrocenyl derivatives with aldehyde 8.
In contrast, the reaction of complex 13 with com-
plexes 11 and 12 were found to be trans configurated.
These complexes differ from 1 and 7 by a direct link
between ferrocene and the carbonyl moiety (Scheme
7).
plex 10 carbanion, gave significant resinification.
The expected product could not be detected. As
observed above, both double bonds created in com-

D. Prim et al. / Journal of Organometallic Chemistry 624 (2001) 124–130
127
It is worthy to note that benzaldehydetricar-
bonylchromium complex 2 is the most electrophilic
candidate under Claisen–Schmidt condensation condi-
tions used in our study. The best results were obtained
in reacting complex 2 with carbanions of ketone 10 or
enones 5 and 6. As soon as the aldehyde function is
moved away from the coordinated cycle such as in
complex 8, the electron withdrawing effect of Cr(CO)3
group is less efficient and yields of condensation de-
creased from 60% for complex 11 to 21% for complex
12. As for the condensation of 8 with enone 5 anion, no
bimetallic complex could be detected in the crude mix-
ture (Scheme 6).
sodium benzophenone ketyl under dry nitrogen. 1H-
and 13C-NMR spectra were obtained with Bruker 200
and ARX 400 spectrometers. Infrared spectra were
recorded with Perkin–Elmer 1420. Melting points were
measured with a Reichert apparatus.
3.2. Preparation of enones 4 and 5
An aqueous solution of KOH (5 ml, 0.474 mmol, 1
M) was added at 0°C to a solution of the organometal-
lic aldehyde (1.153 mmol) in acetone (10 ml). The
reaction mixture was stirred for 1 h at 0°C and poured
into cold water. The precipitate was filtered off and
purified by silica gel chromatography using a mixture
of petroleum ether and ether (9:1) as eluant to afford
the corresponding enone.
In conclusion we have prepared different hetero-
bimetallic complexes by introducing keto-spacers of
various natures. Further work will be directed in the
characterization of the second order polarisability i of
these new bimetallic complexes.
Enone 4: 70% yield.1H-NMR (CDCl3, 200 MHz):
7.03 (d, J=16 Hz, 1H, CHꢀ), 6.50 (d, J=16 Hz, 1H,
CHꢀ), 5.55 (d, J=6 Hz, 2H, C6H5), 5.46 (t, J=6 Hz,
1H, C6H5), 5.34 (t, J=6 Hz, 2H, C6H5), 2.35 (s, 3H).
13C{1H}-NMR (CDCl3, 50 MHz): 231.7 (Cr(CO)3),
197.1 (CO), 140.2 (CHꢀ), 127.5 (CHꢀ), 98.8 (C, C6H5),
93.1, 92.8 and 91.2 (CH, C6H5), 28.1 (CH3). IR
(CH2Cl2) cm−1: 1958, 1892, 1645.
3. Experimental
3.1. General
All experiments were always protected from exposure
to light and oxygen. Workup procedures were done in
air. Tetrahydrofuran (THF) used was distilled from
Enone 5: 88% yield..1H-NMR (CDCl3, 200 MHz):
7.42 (d, J=16 Hz, 1H, CHꢀ), 6.33 (d, J=16 Hz, 1H,
CHꢀ), 4.50 (brs, 2H, C5H4), 4.44 (brs, 2H, C5H4), 4.15
Scheme 7. Condensation of aldehydes with acetylferrocene.

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D. Prim et al. / Journal of Organometallic Chemistry 624 (2001) 124–130
(brs, 5H, C5H5), 2.29 (s, 3H). 13C{1H}-NMR (CDCl3,
50 MHz): 194.0 (CO), 144.1 (CHꢀ), 123.6 (CHꢀ), 78.0
(C, C5H4), 70.2 and 68.7 (CH, C5H4), 67.8 (CH, C5H5),
26.2 (CH3). IR (CH2Cl2) cm−1: 1655.
ation by silica gel chromatography using a mixture of
petroleum ether and ether (98:2) as eluant afforded red
crystals of complex 6.
1
Complex 6: 60% yield.. H-NMR (CDCl3, 200 MHz):
7.60 (s, 1H, CHꢀ), 4.54 (brs, 2H, C5H4), 4.41 (brs, 2H,
C5H4), 4.16 (brs, 5H, C5H5), 2.72 (t, J=5.5 Hz, 2H,
CH2CO), 1.84 (m, 2H, CH2), 1.57 (m, 4H, (CH2)2).
13C{1H}-NMR (CDCl3, 50 MHz): 213.0 (CO), 137.7
3.3. Complex 1 prepared from enone 5
A solution of nBuLi (0.408 ml, 0.613 mmol, 1.6 M) in
THF (5 ml) was added at 0°C, under N2 to (iPr)2NH
(0.0846 ml, 0.645 mmol) in dry THF (3 ml). The
reaction mixture was stirred at 0°C for 10 min and a
solution of complex 3 (184 mg, 0.645 mmol) in dry
THF (3 ml) was added. The resulting mixture was
stirred at 0°C for 45 min. A solution of ferrocenecar-
baxaldehyde (222 mg, 0.774 mmol) in dry THF (3 ml)
was then added dropwise at the same temperature. The
mixture was stirred at room temperature (r.t.) for 24 h,
poured into ice cold water (50 ml) and extracted twice
with diethylether (2×30 ml). The organic phases were
washed with water (2×30 ml), saturated solution of
ammoniumchloride (50 ml) and evaporated to dryness
under reduced pressure. Purifiation by silica gel chro-
matography using a mixture of petroleum ether and
ether (7:3) as eluant afforded red crystals of complex 1.
(C6 H=C), 80.0 (C6 =CH), 74.1 (C, C5H4), 71.4 and 70.9
(CH, C5H4), 69.7 (CH, C5H5), 28.4 (COC6 H2), 20.0,
20.05 and 20.1 (CH2). IR (CH2Cl2) cm−1: 1710.
3.5. Preparation of complex 7
A solution of nBuLi (0.297 ml, 0.474 mmol, 1.6 M) in
THF was added at 0°C, under N2 to (iPr)2NH (0.064
ml, 0.494 mmol) in dry THF (3 ml). After 10 min at
0°C a solution of complex 6 (186 mg, 0.494 mmol) in
dry THF (3 ml) was added and the reaction mixture
was stirred for 45 min at the same temperature. A
solution of tricarbonylchromium benzaldehyde (119
mg, 0.491 mmol) in dry THF (3 ml) was then added
dropwise in 1 h. After 24 h at r.t. the reaction mixture
was poured into ice cold water (50 ml). The organic
layer was extracted twice with water (2×20 ml) and
with a saturated solution of ammoniumchloride (50
ml). The organic phase was dried with MgSO4 and
evaporated under reduced pressure. Purifiation by silica
gel chromatography using a mixture of petroleum ether
and ether (7: 3) as eluant afforded red crystals of
complex 7.
1
Complex 1: 60% yield. H-NMR (CDCl3, 200 MHz):
7.62 (d, J=16 Hz, 1H, CHꢀ), 7.14 (d, J=16 Hz, 1H,
CHꢀ), 6.76 (d, J=16 Hz, 1H, CHꢀ), 6.51 (d, J=16
Hz, 1H, CHꢀ), 5.59 (d, J=6 Hz, 2H, C6H5), 5.36 (m,
3H, CH3), 4.52 (brs, 2H, C5H4), 4.45 (brs, 2H, C5H4),
4.13 (brs, 5H, C5H5). 13C{1H}-NMR (CDCl3, 50 MHz):
232.3 (Cr(CO)3), 187.2 (CO), 147.0 (CHꢀ), 139.4 (CHꢀ),
126.6 (CHꢀ), 123.2 (CHꢀ), 100.0 (C, C6H5), 98.9, 93.3
and 91.5 (CH, C6H5), 77.7 (C, C5H4), 70.3, 69.5 and
69.2 (CH, C5H4, C5H5). M.p.: 92°C. IR (CH2Cl2)
cm−1: 1978, 1900 (Cr(CO)3), 1615 (CO). Anal. Found:
C, 60.41; H, 3.88. Calc. for C24H18O4CrFe: C, 60.28; H,
3.79%.
1
Complex 7: 45% yield.. H-NMR (CDCl3, 200 MHz):
7.63 (s, 1H, CHꢀ), 7.29 (s, 1H, CHꢀ), 5.52 (m, 2H,
C6H5), 5.36 (m, 3H, C6H5), 4.55 (brs, 2H, C5H4), 4.45
(brs, 2H, C5H4), 4.16 (brs, 5H, C5H5), 2.84 (t, J=6 Hz,
2H, CH2), 2.71 (t, J=6 Hz, 2H, CH2), 1.83 (m, 2H,
CH2). 13C{1H}-NMR (CDCl3, 50 MHz): 232.2
(Cr(CO)3), 187.4 (CO), 140.1 (CHꢀ), 139.7 (Cꢀ), 132.1
(CHꢀ), 131.3 (Cꢀ), 94.8, 91.5 and 91.1 (CH, C6H5), 92.8
(C, C6H5), 78.3 (C, C5H4), 71.5 and 71.2 (CH, C5H4),
69.6 (CH, C5H5), 28.5, 28.0 and 22.5 (CH2). IR
(CH2Cl2) cm−1: 1609. Anal. Found: C, 62.41; H, 4.20.
Calc. for C27H22O4CrFe: C, 62.57; H 4.28%.
Complex 1 was also prepared from enone 4 using the
above described procedure.
3.4. Preparation of complex 6
n
A solution of BuLi (1.327 ml, 2.12 mmol, 1.6 M) in
THF was added at 0°C, under N2 to (iPr)2NH (0.3 ml,
2.32 mmol) in dry THF (8 ml). The reaction mixture
was stirred for 10 min at 0°C and added to a solution
of cyclohexanone (0.2 ml, 1.93 mmol) in dry THF (9
ml) at the same temperature. After 45 min at 0°C,
ferrocenecarboxaldehyde (650 mg, 2.32 mmol), in dry
THF (8 ml) was added and the mixture was stirred at
r.t. for 3 h. Diethylether (20 ml) was then added and
the reaction mixture was poured into ice cold water (50
ml). The organic layer was extracted twice with water
(2×20 ml) and with saturated solution of ammonium-
chloride (50 ml). The organic phase was dried with
MgSO4 and evaporated under reduced pressure. Purifi-
3.6. Preparation of complex 8
n
A solution of BuLi (5.41 ml, 9.57 mmol, 1.6 M) in
THF was added at −78°C, under N2 to 2-bromo-5-
dioxolanylthiophene (2.045 g, 8.7 mmol) in dry THF
(10 ml). The reaction mixture was stirred for 1 h at
−78°C and tributylstannylchloride (2.35 ml, 8.7 mmol)
was added. After 1 h and 30 min, water (5 ml) and
diethylether (15 ml) were added. The organic layer was
extracted twice with water (2×20 ml) and a saturated
solution of ammoniumchloride (50 ml). The organic
phase was dried with MgSO4 and evaporated under

D. Prim et al. / Journal of Organometallic Chemistry 624 (2001) 124–130
129
3.7. Preparation of complex 13
reduced pressure. 2-Tributylstannyl-5-dioxolanylthio-
phene was purified by distillation.
2-Tributylstannyl-5-dioxolanylthiophene: 75% yield..
PPh3CHCHO (660 mg, 2.16 mmol) was added in
portions to solution of benzaldehydetricar-
1
a
B.p.4mmHg: 50°C. H-NMR (CDCl3, 200 MHz): 7.26 (d,
bonylchromium (250 mg, 1.032 mmol) in DMF (3 ml)
and the reaction mixture was stirred for 8 h at r.t. An
additional 24 h was necessary to ensure completion of
the reaction. The reaction mixture was poured into
water (50 ml) and extracted twice with diethylether
(2×50 ml). After extraction, the organic phase was
evaporated under reduced pressure and purified by
silica gel chromatography using a mixture of petroleum
ether and ether (6:4) as eluant to afford yellow–orange
crystals of complex 13.
J=3 Hz, 1H, C4H2S), 7.04 (d, J=3 Hz, 1H, C4H2S),
6.10 (s, 1H, CH6 (OCH2)2), 4.08 (m, 2H, OCH2), 3.99 (m,
2H, OCH2), 1.62 (m, 6H, SnCH2), 1.30 (m, 6H, CH2),
1.07 (m, 6H, CH2), 0.88 (m, 9H, CH3). 13C{1H}-NMR
(CDCl3, 50 MHz): 138.8 (C, C4H2S), 135.1 and 127.6
(CH, C4H2S), 116.2 (C, C4H2S), 100.4 (C
65.3 (CH(OCH2)2, 28.9, 27.3 and 13.8 (CH2), 10.8
(CH3).
6 H(OCH2)2),
6
A solution of chlorobenzenetricarbonylchromium
(1.20 g, 4.8 mmol) in degazed THF (10 ml) was added
to Pd2dba3 (0.073 g, 0.08 mmol), AsPPh3 (0.098 g, 0.32
mmol) [10] in degazed THF (5 ml). After 15 min, the
above prepared stannylated thiophene (1.791 g, 4
mmol) was added and the mixture was stirred at r.t. for
18 h. Water (20 ml) and diethylether (20 ml) were
added. The organic layer was extracted twice with
water (2×20 ml) and a saturated solution of ammoni-
umchloride (50 ml). The organic phase was dried with
MgSO4 and evaporated under reduced pressure. Purifi-
ation by silica gel chromatography using a mixture of
petroleum ether and ether (9:1) as eluant afforded the
expected coupling complex.
Complex 13: 77% yield. 1H-NMR (CDCl3, 200
MHz): 9.64 (d, J=7 Hz, 1H, CH
1H, CHꢀ), 6.49 (dd, J=16 Hz, 1H, CH
C6H5), 5.35 (t, J=6 Hz, 2H, C6H5). 13C{1H}-NMR
(CDCl3, 50 MHz): 231.5 (Cr(CO)3), 192.6 (CHO), 149.3
6
O), 6.99 (d, J=16 Hz,
6
6
ꢀ), 5.53 (m, 3H,
6
and 128.5 (CHꢀ), 97.3 (C, C6H5), 93.6, 93.3 and 90.9
(CH, C6H5). IR (CH2Cl2) cm−1: 1978, 1905, 1682.
3.8. Preparation of complexes 11 and 12
A solution of nBuLi (0.236 ml, 0.379 mmol, 1.6 M) in
THF was added at 0°C, under N2 to (iPr)2NH (0.052
ml, 0.395 mmol) in dry THF (2.5 ml). The reaction
mixture was stirred for 10 min at 0°C and a solution of
acetylferrocene (80 mg, 0.395 mmol) in dry THF (2 ml)
was added dropwise. After 45 min at 0°C, a solution of
the appropriate aldehyde (0.474 mmol) in dry THF (2
ml) was added dropwise. The mixture was stirred at r.t.
for 24 h and poured into water (50 ml). The organic
layer was extracted twice with water (2×20 ml) and a
saturated solution of ammoniumchloride (50 ml). The
organic phase was dried with MgSO4 and evaporated
under reduced pressure. Purifiation by silica gel chro-
matography using a mixture of petroleum ether and
ether (7:3) as eluant afforded red crystals of the ex-
pected complex.
2-[(h6-Chlorobenzene)tricarbonylchromium]-5-dioxo-
lanylthiophene: 60% yield.. 1H-NMR (CDCl3, 200
MHz): 7.15 (d, J=4 Hz, 1H, C4H2S), 7.07 (d, J=4 Hz,
1H, C4H2S), 6.06 (s, 1H, CH6 (OCH2)2), 5.66 (d, J=6
Hz, 2H, C6H5), 5.44 (t, J=6 Hz, 2H, C6H5), 5.28 (t,
J=6 Hz, 1H, C6H5), 4.09 (m, 2H, OCH2), 3.99 (m, 2H,
OCH2). 13C{1H}-NMR (CDCl3, 50 MHz): 233.0
(Cr(CO)3), 143.1 and 140.6 (C, C4H2S), 126.9 and 124.8
(CH, C4H2S), 100.1 (C
91.1 and 90.5 (CH, C6H5), 65.4 (CH(OC
6
H(OCH2)2), 99.6 (C, C6H5), 92.3,
H2)2.
6
An aqueous solution of HCl (50 ml, 1 mol l−1) was
added to 2-[(h6-chlorobenzene) tricarbonylchromium]-
5-dioxolanylthiophene (0.061 g, 0.16 mmol) in di-
ethylether (5 ml) and water (5 ml). After 5 h, an
aqueous solution of Na2CO3 (30 ml, 1 mol l−1) was
added. The aqueous phase was extracted with di-
ethylether (2×50 ml). The combined organic phases
were dried with MgSO4 and evaporated under reduced
pressure. Purifiation by silica gel chromatography using
a mixture of petroleum ether and ether (7:3) as eluant
afforded complex 8.
Complex 11: 60% yield.. 1H-NMR (CDCl3, 200
MHz): 7.28 (d, J=16 Hz, 1H, CH=), 6.90 (d, J=16
Hz, 1H, CH=), 5.66 (d, J=6 Hz, 2H, C6H5), 5.41 (m,
3H, C6H5), 4.88 (brs, 2H, C5H4), 4.62 (brs, 2H, C5H4),
4.21 (brs, 5H, C5H5). 13C{1H}-NMR (CDCl3, 50 MHz):
232.1 (Cr(CO)3), 191.7 (CO), 137.5 (CHꢀ), 123.8 (CHꢀ),
99.7 (C, C6H5), 93.3, 93.1 and 91.4 (CH, C6H5), 80.1
(C, C5H4), 73.3 (CH, C5H4), 70.4 (CH, C5H4); 69.8
(CH, C5H5). IR (CH2Cl2) cm−1: 1975, 1900, 1648.
Anal. Found: C, 58.24; H, 3.42. Calc. for
C22H16O4CrFe: C, 58.43; H, 3.57%.
1
Complex 8: 67% yield. H-NMR (200 MHz, CDCl3):
9.88 (s, 1H, CH6 O), 7.69 (d, J=4 Hz, 1H, C4H2S), 7.36
Complex 12: 21% yield.. 1H-NMR (CDCl3, 200
MHz): 7.79 (d, J=16 Hz, 1H, CHꢀ), 7.45 (d, J=4 Hz,
1H, C4H2S), 7.50 (d, J=4 Hz, 1H, C4H2S), 7.17 (d,
J=16 Hz, 1H, CHꢀ), 6.16 (d, J=7 Hz, 2H, C6H5),
5.83 (m, 3H, C6H5), 4.99 (brs, 2H, C5H4), 4.77 (brs, 2H,
(d, J=4 Hz, 1H, C4H2S), 5.75 (d, J=6 Hz, 2H, C6H5),
5.42 (m, 3H, C6H5). 13C{1H}-NMR (CDCl3, 50 MHz):
231.8 (Cr(CO)3), 182.6 (C6 HO), 149.8 and 143.2 (C,
C4H2S), 136.6 and 125.5 (CH, C4H2S), 99.8 (C, C6H5),
92.0, 91.6 and 91.1 (CH, C6H5).

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D. Prim et al. / Journal of Organometallic Chemistry 624 (2001) 124–130
C5H4), 4.24 (brs, 5H, C5H5). 13C{1H}-NMR (CDCl3, 50
MHz): 232.5 (Cr(CO)3), 192.3 (CO), 141.9 and 141.3
(C, C4H2S), 132.5 and 132.1 (CH, C4H2S), 125.8 (CHꢀ),
122.8 (CHꢀ), 101.8 (C, C6H5), 94.9, 92.4 and 90.4 (CH,
C6H5), 80.5 (C, C5H4), 72.9 (CH, C5H4), 70.2 (C,
C5H4), 69.7 (C, C5H5). IR (CH2Cl2) cm−1: 1968, 1889,
1651. Anal. Found: C, 58.25; H, 3.21. Calc. for
C26H18O4SCrFe: C, 58.44; H, 3.40%.
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Acknowledgements
We thank CNRS and the EU Training and Mobility
of Researchers program for financial support and for a
postdoctoral fellowship to Z.F.P.
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