Metal carbonyl complexes of the ditertiary bismuthine p-Ph2BiC6H4BiPh2 and the effect of coordination upon bismuthine ligand geometry

Article abstract of DOI:10.1016/S0022-328X(99)00134-5

Complexes of the type [M(CO)₅(p-Ph₂BiC₆H₄BiPh ₂)] and [{M(CO)₅}₂(p-Ph₂BiC₆H ₄BiPh₂)] (M = Cr or W) have been prepared and characterised by chemical analysis, ¹H- and ¹³C{¹H}-NMR and IR spectroscopies. The crystal structure of p-Ph₂BiC₆H₄BiPh₂ is reported. The reaction of [CpFe(CO)₂(THF)]⁺ with p-Ph₂BiC₆H₄BiPh₂ in refluxing CH₂Cl₂ results in cleavage of one Bi-C bond to form [CpFe(CO)₂(BiPh₃)]⁺ identified by an X-ray study. A survey of BiPh₃ and its compounds has established that the C-Bi-C angles increase upon complex formation.

Full text of DOI:10.1016/S0022-328X(99)00134-5

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Journal of Organometallic Chemistry 584 (1999) 179–184
Metal carbonyl complexes of the ditertiary bismuthine
p-Ph2BiC6H4BiPh2 and the effect of coordination upon bismuthine
ligand geometry
Nicholas J. Holmes, William Levason *, Michael Webster
Department of Chemistry, Uni6ersity of Southampton, Southampton SO17 1BJ, UK
Received 25 January 1999; received in revised form 24 February 1999
Abstract
Complexes of the type [M(CO)5(p-Ph2BiC6H4BiPh2)] and [{M(CO)5}2(p-Ph2BiC6H4BiPh2)] (M=Cr or W) have been prepared
and characterised by chemical analysis, 1H- and 13C{1H}-NMR and IR spectroscopies. The crystal structure of p-Ph2BiC6H4BiPh2
is reported. The reaction of [CpFe(CO)2(THF)]+with p-Ph2BiC6H4BiPh2 in refluxing CH2Cl2 results in cleavage of one Bi–C
bond to form [CpFe(CO)2(BiPh3)]+identified by an X-ray study. A survey of BiPh3 and its compounds has established that the
C–Bi–C angles increase upon complex formation. © 1999 Elsevier Science S.A. All rights reserved.
Keywords: Bismuthine; Chromium; Tungsten; X-ray structure
1. Introduction
2. Results and discussion
The coordination chemistry of tertiary bismuthine
ligands is very limited, a reflection both of the very
weak s-donor ability of the bismuth and the ease with
which Bi–C bonds break in the presence of many metal
centres [1,2]. Even for the commonest ligand, BiPh3,
only five complexes have been characterised by X-ray
crystallography, namely -[Cr(CO)5(BiPh3)] [3], [M-
(CO)5(BiPh3)] (M=Mo or W) [4], [(h5-C5H5)Fe(CO)2-
(BiPh3)]BF4 [5], and [{Cr(CO)3(h6-Ph)}2BiPh] [6], the
last containing the bismuthine bonded to chromium h6
via the phenyl rings not via the bismuth. Although
potential ligands containing two bismuth atoms have
been prepared, there are no reports of metal complexes
[1]. There are also polydentates containing one bismuth
centre in combination with P or As donors [1]. We
report here attempts to prepare complexes of the diter-
tiary bismuthine p-Ph2BiC6H4BiPh2. We recently re-
ported that coordination of SbPh3 to metal centres
resulted in an increase in the C–Sb–C bond angles and
a decrease in the Sb–C bond distances [7], and we have
used literature data to look for similar trends in bis-
muthine complexes.
2.1. Reactions of BiPh3 with metal carbonyls
In an attempt to extend the number of BiPh3 com-
plexes to support our search for systematic changes in
the geometry at bismuth on coordination, we examined
the reactions of BiPh3 with Ni(CO)4, Co2(CO)8,
Fe(CO)5, Fe2(CO)9/THF and Mn2(CO)10 using condi-
tions which successfully produce the corresponding
SbPh3 complexes [1]. The reactions were monitored in
situ by IR spectroscopy of the solutions in the carbonyl
region. No reaction was apparent between Ni(CO)4 and
BiPh3 in CH2Cl2, the reagents being recovered un-
changed after several hours, consistent with the report
of Benlian and Bigorgne [8]. In contrast, a mixture of
Co2(CO)8 and BiPh3 in CH2Cl2 darkened and decom-
posed over a few hours, but without any IR spectro-
scopic
evidence
for
the
formation
of
Co2(CO)8-n(BiPh3)n, the w(CꢀO) of the binary carbonyl
simply diminishing over time with no new bands ap-
pearing. No reaction was apparent between Fe(CO)5
and BiPh3 using [{CpFe(CO)2}2] or NaBH4 as catalyst,
whilst photolysis in toluene resulted in decomposition.
Decomposition also occurred using Fe2(CO)9/THF. It
* Corresponding author. Fax: +44-1703-593781.
appears that the old report [9] of
a
(20e)
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00134-5

180
N.J. Holmes et al. / Journal of Organometallic Chemistry 584 (1999) 179–184
Fe(CO)4(BiPh3)2 is erroneous. We have recently pre-
pared [Mn2(CO)10−n(SbPh3)n] (n=1 or 2) by photoly-
sis of Mn2(CO)10/SbPh3 in toluene or from Mn2-
(CO)10/SbPh3/Me3NO [10]. In similar reactions using
BiPh3 only decomposition products were detected by in
situ IR spectroscopic studies.
There is some disagreement in the literature about
the 13C{1H}-NMR spectrum of BiPh3 concerning the
assignment of the ipso-carbon resonance, which is vari-
ously described as l 131.1, 134.1 or 155.4 ppm [11,12].
Similar uncertainties surround the ipso-carbon reso-
nance positions in the metal complexes [4,5], and fur-
ther confusion can be introduced by the facile
decomposition of the metal complexes in solution. Clar-
ification of this point was important in connection with
the spectra of the dibismuthine complexes in Section
2.3. Our 13C{1H}-NMR spectra of BiPh3 (purified by
repeated recrystallisations) confirm the report [12] that
the ipso-carbon resonance is at l 155.5 (CHCl3 solu-
tion). In the complexes (recorded in CH2Cl2/CDCl3
solutions at 250 K to minimise decomposition) the
ipso-carbon resonances were observed at l 156.3
[Cr(CO)5(BiPh3)], 155.0 [Mo(CO)5(BiPh3)], 156.7 [W-
(CO)5(BiPh3)] and 156.0 [(h5-C5H5)Fe(CO)2(BiPh3)]-
BF4.
Fig. 1. Molecular structure of p-Ph2BiC6H4BiPh2 showing the atom
numbering scheme. Thermal ellipsoids are drawn at the 50% proba-
bility level.
2.2. The p-Ph2BiC6H4BiPh2 ligand
(THF)] (generated in situ by photolysis of W(CO)6 in
THF) in 1:1 and 1:2 mole ratios, followed by removal
of the THF in vacuo, and recrystallisation of the prod-
ucts by cooling a hexane solution produced yellow
The p-Ph2BiC6H4BiPh2 was prepared as described by
Zorn et al. [13] by reaction of p-C6H4Br2, BuLi and
Ph2BiCl, and purified by recrystallisation from propan-
2-ol. After completion of our work, Matano et al. [14]
n
solids
[W(CO)5(p-Ph2BiC6H4BiPh2)]
(1)
and
[{W(CO)5}2(p-Ph2BiC6H4BiPh2)] (2), respectively. The
IR spectra in n-hexane solution are typical of W(CO)5
groups with w(CꢀO) at 2073, 1948 cm−1 (1) and 2075,
1950 cm−1 (2), which are as expected very similar to
reported
the
preparations
of
m-
and
p-
Ph2BiC6H4BiPh2, and higher oligomers Ph2BiC6H4(Bi-
PhC6H4)nBiPh2 (n=1 or 2). The latter syntheses used
different reagents and reaction conditions, and in our
preparations only BiPh3 and p-Ph2BiC6H4BiPh2 were
obtained in isolable amounts, although traces of
Ph2BiC6H4BiPhC6H4BiPh2 were sometimes detected in
the crude product by FAB MS. The p-Ph2BiC6H4BiPh2
Table 1
a
,
Selected bond lengths (A) and angles (°) for p-Ph2BiC6H4BiPh2
1
was characterised by analysis, H- and 13C{1H}-NMR
spectroscopy (Section 3). Notably the 13C{1H}-spec-
trum contains six resonances, 155.4, 155.2 (ipso), 139.8
(C6H4), 137.9 (o-Ph), 130.8 (m-Ph), 128.0 (p-Ph). The
X-ray crystal structure of the ligand was obtained and
is shown in Fig. 1 and selected bond lengths and angles
are given in Table 1. The structure consists of discrete
centrosymmetric molecules with the expected pyramidal
geometry at the Bi atom. The C–Bi–C angles are close
to those found in BiPh3 [15,16] and the Bi–C distances
although not well determined fall in the expected range;
other geometrical features are unexceptional.
,
Bond length (A)
Bi–C(1)
Bi–C(11)
Bi–C(21)
2.25(2)
2.24(2)
2.26(2)
1.36(2)
C(1)–C(2)
C(1)–C(3)
C(2)–C(3i)
1.35(2)
1.38(2)
1.42(2)
C–C (phenyl)
–1.43(2)
Bond angle (°)
C(1)–Bi–C(11)
C(1)–Bi–C(21)
C(11)–Bi–C(21)
C–C–C (phenyl)
93.4(6)
93.9(6)
94.3(6)
C(2)–C(1)–C(3)
C(1)–C(2)–C(3i)
C(1)–C(3)–C(2i)
119(2)
122(1)
119(1)
118(2)–122(2)
Torsional angle (°)
C(1)–Bi–C(11)–C(12)
C(1)–Bi–C(21)–C(22)
−5(1)
−96(1)
C(2)–C(1)–Bi–C(11) −83(1)
C(2)–C(1)–Bi–C(21) 11(1)
2.3. p-Ph2BiC6H4BiPh2 complexes
a Symmetry operation: (i) 1−x, −y, 1−z.
The reaction of p-Ph2BiC6H4BiPh2 with [W(CO)5-

N.J. Holmes et al. / Journal of Organometallic Chemistry 584 (1999) 179–184
181
the frequencies observed for [W(CO)5(BiPh3)] (2074,
to record the 13C{1H}-NMR spectrum, 3 decomposes
to 4 and Cr(CO)6. Mass balance requires other prod-
ucts to form but these were not identified, presumably
being in the observed precipitate. Decomposition/dis-
proportionation is also a feature of the Group 6 car-
bonyl chemistry of distibines such as Ph2SbCH2SbPh2
[17,18]. All attempts to isolate molybdenum carbonyl
complexes of p-Ph2BiC6H4BiPh2 were unsuccessful, the
reaction mixtures of [Mo(CO)5(THF)] and the ligand
rapidly turning brown and then black, and even at low
temperatures no complex could be isolated. The solu-
tion stability of the Group 6 carbonyl complexes
[M(CO)5(BiPh3)] is W\CrꢀMo [4], and our results
indicate a similar order for the p-Ph2BiC6H4BiPh2 com-
plexes, although these are all less stable than the BiPh3
analogues.
In an attempt to improve stability/solubility, we tried
to prepare [(h5-C5H5)Fe(CO)2(p-Ph2BiC6H4BiPh2)]BF4,
from reaction of [(h5-C5H5)Fe(CO)2(THF)]+and the
ligand. No reaction was apparent after stirring a sus-
pension of the reagents in Et2O overnight at room
temperature (r.t.) Similarly no reaction (as monitored
by IR spectroscopy) occurred in CH2Cl2 at r.t., but on
refluxing the CH2Cl2 solution for several hours, the CO
bands of the starting material disappeared, and were
replaced by two new bands. Work up gave a quantity
of brown/black material and an orange solid. Crystals
of the latter were grown by the vapour diffusion of
diethyl ether into a dichloromethane solution and
found by an X-ray crystal structure determination to be
the known complex [(h5-C5H5)Fe(CO)2(BiPh3)]BF4 [5]
although as a different polymorph [19]. Cell reduction
to the Niggli form established that the crystals were
different, although the cell volumes are very similar and
the geometry of the cation is very similar to that in the
published structure [5]. The possibility that the crystal
studied was unrepresentative of the whole was elimi-
nated since the 13C{1H}-NMR and the IR spectra of
other crystals from the batch and the bulk powder were
identical, and in excellent agreement with literature
data on the BiPh3 complex [5]. Similarly the possibility
that it results from BiPh3 impurity in the p-
Ph2BiC6H4BiPh2 was ruled out since, (a) the same batch
used to obtain W and Cr complexes was used for the
iron complex; and (b) the yield is not consistent with a
minor impurity. The generation of BiPh3 from p-
Ph2BiC6H4BiPh2 requires only that one weak C–Bi
bond on the bridging p-phenylene group breaks and a
hydrogen atom is picked up by the carbon. Fission of
C–Bi bonds in the presence of metals is well estab-
lished, although often the decomposition products were
not identified [1,2]. A closer example of ligand modifi-
cation and coordination is in the formation of
1
1945 cm−1) [4]. The H-NMR spectra are uninforma-
tive, but the 13C{1H}-NMR are more useful. NMR
spectra were recorded from CH2Cl2/CDCl3 solutions at
250 K to minimise decomposition. For the monotung-
sten complex (1), the l(CO) were found at 198.4 {1JW–
C=176 Hz} and 197.5 {1JW–C=122 Hz}, the ipso-Cs
at 157.6, 156.0, 155.6, and 155.1, and seven other
aromatic resonances between 140 and 128 ppm (by
symmetry for an h1 dibismuthine we expect 4 ipso-Cs
and 8 others). The ditungsten complex 2 was less
soluble and the 13C{1H}-NMR spectra had poorer sig-
1
nal/noise and the JW–C satellites were unclear on the
l(CO) resonances. However the aromatic regions are
notably simpler than in complex 1 with two ipso-C
resonances 156.0, 155.5, and four others. In contrast to
[W(CO)5(BiPh3)] which exhibited a parent ion and step-
wise loss of COs in the FAB mass spectrum, the
dibismuthine complexes gave very weak FAB data
dominated by lower mass fragments and are not useful.
Despite many attempts we have been unable to obtain
X-ray quality crystals of either tungsten complexes,
even at low temperatures slow decomposition occurs in
solution.
The chromium complexes of p-Ph2BiC6H4BiPh2 are
less stable in solution than the tungsten analogues,
although the powders appear stable at −20°C under
nitrogen for some months. The reaction of
[Cr(CO)5(THF)] with p-Ph2BiC6H4BiPh2 in a 2:1 mole
ratio, followed by rapid removal of the THF in vacuo,
and recrystallisation by cooling a hexane solution, gave
a poorly soluble greenish yellow powder, identified by
analysis as [{Cr(CO)5}2(p-Ph2BiC6H4BiPh2)] (3). The
filtrate contained the paler yellow [Cr(CO)5(p-
Ph2BiC6H4BiPh2)] (4) and Cr(CO)6 which were again
separated by crystallisation from hexane with cooling.
Better yields of 4 were obtainable directly using a 1:1
ratio of [Cr(CO)5(THF)]: p-Ph2BiC6H4BiPh2. The IR
spectrum of complex 4 in n-hexane (w(CꢀO) 2064, 1948
cm−1) and its 13C{1H}-NMR spectrum, which was very
similar to that of 1, confirm it as having h1-dibis-
muthine coordination. The freshly prepared n-hexane
solution of complex 3 had a very similar IR spectrum
(2064, 1948 cm−1) to 4, but its 13C{1H}-NMR spec-
trum was initially confusing, showing a complex aro-
matic region (at least 10 resonances), and three l(CO)
(212.0, 216.9, 221.1), and after recording the spectrum
some precipitate was evident in the NMR tube. An IR
spectrum obtained from the NMR solution after
recording the NMR data revealed three w(CꢀO)
stretches, one of which corresponded to Cr(CO)6. The
13C{1H}-NMR resonance at 212.0 can also be identified
as the hexacarbonyl, and comparison of the aromatic
region of the spectrum obtained from 3 showed it was
very similar indeed to that of 4. We conclude that, in
solution at 250 K over a period of the few hours needed
[Pd(AsMe2Ph)3Cl]BPh4
on
reaction
of
Bi(o-
C6H4AsMe2)3 with PdCl2(MeCN)2 and NaBPh4 [20].

182
N.J. Holmes et al. / Journal of Organometallic Chemistry 584 (1999) 179–184
sions, albeit at lower confidence limits, with the small
samples. As with SbPh3 where the sample size is much
larger, the effect of coordination at the Bi centre is to
increase the C–Bi–C angle. For each complex a mean
C–Bi–C angle was obtained and the mean of these
(mean) angles was 99.1(9)°.1 Similarly for the uncom-
plexed Bi ligand where we took the four examples gives
a mean C–Bi–C angle of 93.9(1)°. (Using only the two
BiPh3 structures did not effect the conclusion.) In an
attempt to quantify the difference in the means we used
two statistical tests [21] (Student’s t-test for two sam-
ples with different variances (t=12.5, d.f.=4) and
ANOVA for a single factor (F=122, d.f.=1, 7)),
which allows us to reject the Null Hypothesis (that is,
that the two samples are drawn from a common popu-
lation) at better than h=0.01. We also used the non-
parametric Mann–Whitney U-test [22] and as expected
found a similar result. With the usual caveats, we
conclude that the effect of the increasing bond angle on
coordination is statistically significant. No relationship
between the C–Bi–C angle and the Bi–C distance
analogous to that proposed [7] for Sb was found in the
sample studied.
Fig. 2. Scattergram plot showing the average C–Bi–C angle (°)
,
against the average Bi–C bond length (A) for substituted aryl bis-
muthines BiR3.
During this study we examined the pyramidal aryl
substituted bismuthines BiAr3 in the Cambridge struc-
tural database [23–25] and noted a positive correlation
between the mean C–Bi–C angle and the mean Bi–C
distance for 15 fragments. This is shown in Fig. 2 and
the product–moment correlation coefficient (0.83) and
the Spearman rank correlation coefficient (0.68)
provide numerical support for the graphical display. Li
et al [26] suggested such a trend based on four
examples.
It is clear from the above results that p-
Ph2BiC6H4BiPh2 is not well suited as a ligand with
which to develop coordination chemistry of dibismuthi-
nes, in that in addition to very poor donor properties
and the lack of substituents suited to NMR studies
(both evident when the work was initiated), the com-
plexes have poorer solubilities and are more prone to
Bi–C fission than the BiPh3 analogues. Future studies
will focus on alkyl substituted dibismuthines.
2.4. The effect of coordination on bismuth ligand
geometries
3. Experimental
Physical measurements were made as described previ-
ously [4].
As indicated in Section 1, one object of this study
was to obtain structural data on one or more complexes
of p-Ph2BiC6H4BiPh2 and examine the bond angle/
bond length changes that occur at the bismuth centre
on coordination. Our failure to obtain crystallographic
data on any of the complexes prevents this, but we have
used literature data on BiPh3 complexes as an alterna-
tive. Some five complexes of BiPh3 have been struc-
turally characterised including the Fe compound
polymorph noted here and the ligand itself has been
reported on two occasions [15,16] providing very small
samples for any statistical inference to be drawn. In
addition there is the dibismuthine reported here and the
3-coordinate Bi complex [{Cr(CO)3(h6-Ph)}2BiPh] [6],
both of which have C–Bi–C angles close to those in
BiPh3. The poor donor properties of the bismuthines
make it unlikely that there will be large numbers of
examples available and we are forced to draw conclu-
3.1. Synthesis
3.1.1. p-Ph2BiC6H4BiPh2
p-C6H4Br2 (3.14 g, 13.3 mmol) in diethyl ether (40
ml) and nBuLi (53.3 mmol) were refluxed together
under nitrogen for 165 min. After cooling, BiPh2Br
(11.8 g, 26.6 mmol) suspended in diethyl ether (60 ml)
was added and the mixture stirred overnight and then
refluxed under nitrogen for 9 h. After cooling, water (30
ml) was added and the organic layer separated, the
solvent removed and propan-2-ol (50 ml) added to give
a white solid, which was filtered and dried in vacuo.
1 In this and subsequent average values, an unweighted mean was
used and the figure in parentheses represents the sample standard
deviation.

N.J. Holmes et al. / Journal of Organometallic Chemistry 584 (1999) 179–184
183
Yield, 3.5 g, 33%. (Found: C, 45.1; H, 2.8. C30H24Bi2
(Rint=0.064) and an empirical „-scan absorption was
applied (Transmission: min. 0.612; max. 1.000) but no
decay correction was required. The structure was solved
by standard heavy atom procedures and refined to
convergence by full-matrix least-squares refinement on
F [27] to R=0.045 [1431 observed reflections (F\
4|(F)), 145 parameters, anisotropic (Bi, C) and
isotropic atoms (H), w−1=s2(Fo), max. shift/Esti-
mated S.D., 0.002, S=2.0, wR=0.050]. H atoms were
included in the model in calculated positions (d(C–
1
requires C, 44.9; H, 3.0%). H-NMR (CDCl3) 7.2(m),
7.8(m). 13C{1H}-NMR (CHCl3, 300 K) 155.4, 155.2,
139.8, 137.9, 130.8, 128.0.
3.1.2. [W(CO)5(p-Ph2BiC6H4BiPh2)] (1)
W(CO)6 (0.27 g, 0.75 mmol) in THF (30 ml) was
photolysed for 160 min under nitrogen. p-
Ph2BiC6H4BiPh2 (0.60 g, 0.75 mmol) was added and the
mixture refluxed for 5 min. The solvent was then re-
moved, the residue extracted into hexane, filtered, re-
duced in volume to ca. 5 ml and left in the freezer
under nitrogen. The yellow solid which precipitated was
filtered and dried in vacuo. (Found: C, 37.6; H, 2.3.
C35H24Bi2O5W requires C, 37.3; H, 2.1%). 1H-NMR
(CDCl3) 7.2–7.9 (m). 13C{1H}-NMR (CH2Cl2/CDCl3,
250 K) 198.4 {1JW–C=176 Hz} and 197.5 {1JW–C=122
Hz}, 157.6, 156.0, 155.6, 155.1, 140.0, 139.3, 138.0,
136.4, 131.5, 130.3, 128.3. IR (hexane)/cm−1 2073,
1948.
,
H)=0.95 A). The residual electron density was in the
−3
,
range 2.2 to −2.2 e A
.
3.2.1. Crystal data for p-Ph2BiC6H4BiPh2
Molecular formula, C30H24Bi2, Mr=802.48, mono-
clinic, space group, P21/a (no. 14), a=6.849(2), b=
,
22.972(2), c=8.212(1) A, b=97.07(2)°, V=1282.2(4)
3
A , Z=2, Dcalc. =2.078 g cm−3, F(000)=740, v=
,
136.81 cm−1
.
3.1.3. [{W(CO)5}2(p-Ph2BiC6H4BiPh2)] (2)
Same as for 1 using p-Ph2BiC6H4BiPh2 (0.30 g, 0.37
mmol) and refluxing for 1 h. (Found: C, 33.4; H, 1.9.
4. Supplementary material
1
Crystallographic data (excluding structure factors)
for the structures in this paper have been deposited
with the Cambridge Crystallographic Data Centre as
supplementary publication nos. CCDC 114359 (ligand)
and 114360 (Fe complex). Copies of these data can be
obtained free of charge, on application to CCDC, 12
Union Rd., Cambridge CB2 1EZ, UK.
C40H24Bi2O10W2 requires C, 33.1; H, 1.7%). H-NMR
(CDCl3) 7.2–7.9 (m). 13C{1H} NMR (CH2Cl2/CDCl3,
250 K) 197.9 and 197.7, 156.0, 155.5, 138.0, 136.2,
131.0, 130.1. IR (hexane)/cm−1 2075, 1950.
3.1.4. [{Cr(CO)5}2(p-Ph2BiC6H4BiPh2)] (3)
Same as for 2 but using Cr(CO)6 (0.17 g, 0.75 mmol).
(Found: C, 40.0; H, 2.1. C40H24Bi2Cr2O10 requires C,
40.5; H, 2.0%). 1H-NMR (CDCl3) 7.2–7.9 (m).
13C{1H}-NMR (CH2Cl2/CDCl3, 250 K) see text. IR
(hexane)/cm−1 2064, 1948.
Acknowledgements
We thank the EPSRC for support (N.J.H.), for funds
to purchase the diffractometer and for access to the
Chemical Database Service at Daresbury. We also
thank A.R.J. Genge for assistance with the X-ray work.
3.1.5. [Cr(CO)5(p-Ph2BiC6H4BiPh2)] (4)
Same as for 1 but using Cr(CO)6 (0.17 g, 0.75 mmol).
(Found: C, 42.5; H, 2.4. C35H24Bi2CrO5 requires C,
42.3; H, 2.4%). 1H-NMR (CDCl3) 7.2–7.9 (m).
13C{1H}-NMR (CH2Cl2/CDCl3, 250 K) 221.1, 216.9,
155.5, 155.2, 154.9, 139.9, 139.6, 139.3, 137.5, 130.5,
129.5, 127.8. IR (hexane)/cm−1 2064, 1948. Yields for
compounds 1 to 4 range from 10 to 20%.
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Trans. (1998) 3457.
Air-stable crystals were obtained by liquid diffusion
of ethanol into
Ph2BiC6H4BiPh2, and one (0.33×0.22×0.22 mm) was
mounted on a glass fibre using the oil-film technique
and held at 150 K using an Oxford Cryosystems low
temperature device. Data (2519 observations, 2qmax
50°) were recorded using a Rigaku AFC7S diffractome-
ter fitted with Mo–Ka radiation (u=0.71073 A). After
data processing there were 2321 unique observations
a
CH2Cl2 solution of p-
=
,
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observations=4594; No. of unique observations=4320 (Rint
0.050); „-scan absorption correction (T 1.000 (max)–0.476
=
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,
(min)); No. of parameters=307; u (Mo–Ka)=0.71073 A; v=
78.16 cm−1; S=1.47; Max. shift/Estimated S.D., 0.009; R (Fo\
4|(Fo))=0.0468; wR(Fo\4|(Fo))=0.0492.
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[19] Crystal structure of [(h5-C5H5)Fe(CO)2(BiPh3)]BF4. Experimen-
tal details are as given for p-Ph2BiC6H4BiPh2. Crystals were
grown by vapour diffusion of diethyl ether into a CH2Cl2
solution
of
the
compound.
Empirical
formula,
(
C25H20BBiF4FeO2; Mr=704.06; triclinic; space group P1 (no.
,
2); a=9.888(3), b=12.989(5), c=9.700(2) A, h=95.58(3), i=
3
,
96.17(2), k=96.62(3)°, V=1222.7(7) A ; T=150 K; Dcalc.
1.912 Z=2; F(000)=672; Total no. of
=
g
cm−3
;
.