Bridging cyclopentadienyl M-Sn(IV) bonded polymetallic complexes: X-ray crystal structures of [(Me2SnCl)(CO)3MoC5H4C(O)CH 2]2·CH2Cl2 and [(Ph3Sn)(CO)3 WC5H4C(O)CH2]2·3H 2O

Article abstract of DOI:10.1016/S0277-5387(00)00647-1

The dianions [(CO)₃MC₅H₄C(O)CH₂]₂ ^2- reacted with R_nSnX_4-n in a 1:2 or 1:1 ratio to give tetranuclear complexes [(R_nSnX_3-n)(CO)₃MC₅H₄ C(O)CH₂]₂ (M = Mo or W; R = Ph or Me; X = Cl or Br; n = 2 or 3), which have been characterized by elemental analysis. ¹H NMR and IR spectroscopy. The electron-withdrawing groups on the cyclopentadienyl rings greatly decrease the nucleophilicity of the metallic anions. Thus, only one halogen atom on tin was replaced by the metallic anion when the dianions reacted with SnR₂X₂. The crystal structures of complexes 4 (M = Mo; R = Me; X = Cl; n = 2) and 5 (M = W; R = Ph; n = 3) were determined by X-ray crystallography, indicating that both Mo and W atoms adopt a 3:4 piano stool structure, and the Sn-M bond length is 2.7755(3) ? in complex 4 (Sn-Mo) and 2.8154(7) ? in complex 5 (Sn-W).

Full text of DOI:10.1016/S0277-5387(00)00647-1

www.elsevier.nl/locate/poly
Polyhedron 20 (2001) 403–408
Bridging cyclopentadienyl MꢀSn(IV) bonded polymetallic
complexes: X-ray crystal structures of
[(Me2SnCl)(CO)3MoC5H4C(O)CH2]2·CH2Cl2 and
[(Ph3Sn)(CO)3WC5H4C(O)CH2]2·3H2O
Liang-Fu Tang *, Jian-Fang Chai, Zhi-Hong Wang, Wen-Li Jia, Ji-Tao Wang
State Key Laboratory of Elemento-Organic Chemistry, Department of Chemistry, Nankai Uni6ersity, Tianjin 300071, People’s Republic of China
Received 7 August 2000; accepted 23 October 2000
Abstract
The dianions [(CO)3MC5H4C(O)CH2]22− reacted with RnSnX4−n in a 1:2 or 1:1 ratio to give tetranuclear complexes
[(RnSnX3−n)(CO)3MC5H4C(O)CH2]2 (M=Mo or W; R=Ph or Me; X=Cl or Br; n=2 or 3), which have been characterized
by elemental analysis, 1H NMR and IR spectroscopy. The electron-withdrawing groups on the cyclopentadienyl rings greatly
decrease the nucleophilicity of the metallic anions. Thus, only one halogen atom on tin was replaced by the metallic anion when
the dianions reacted with SnR2X2. The crystal structures of complexes 4 (M=Mo; R=Me; X=Cl; n=2) and 5 (M=W;
R=Ph; n=3) were determined by X-ray crystallography, indicating that both Mo and W atoms adopt a 3:4 piano stool
,
,
structure, and the SnꢀM bond length is 2.7755(3) A in complex 4 (SnꢀMo) and 2.8154(7) A in complex 5 (SnꢀW). © 2001 Elsevier
Science B.V. All rights reserved.
Keywords: Cyclopentadienyl; Molybdenum; Tungsten; Tin; X-ray crystal structure
1. Introduction
the ring, the reactivity and physical properties of substi-
tuted cyclopentadienyl complexes are also very different
from the unsubstituted analogues [7]. Many MꢀSn
bonded complexes containing the cyclopentadienyl lig-
and have also been prepared by salt elimination reac-
tions in good yields [8], some of which have proved to
be very active and selective for catalyzed olefin
metathesis [9]. Our group has been interested in study-
ing the MꢀSn bonded bimetallic complexes in recent
years [10,11]. We found that the electronic effect of
substituents on cyclopentadienyl ligands has a great
influence on the nucleophilicity of cyclopentadienyl
metal anions [12]. In this paper, we describe the exten-
sion of the previous work and report the synthesis of
bridging cyclopentadienyl MꢀSn (M=Mo or W)
bonded polynuclear complexes. The dianions
[(CO)3MC5H4C(O)CH2]22− reacted with RnSnX4−n to
The chemistry of MꢀSn(IV) bonded complexes has
been the object of extensive studies owing to their
applications in many catalytic and stoichiometric pro-
cesses [1–4]. These complexes have direct bonding be-
tween different metals and hence may show different
reactivities from those of mononuclear complexes [5,6].
The synthesis and reactivity of such compounds consti-
tute an active area in organometallic chemistry. There
are several synthetic methods for obtaining such com-
plexes, such as oxidative addition and nucleophilic dis-
placement reactions.
The cyclopentadienyl ligand has played an important
role in the development of transition metal chemistry.
As the electronic and steric characteristics of the ligand
can easily be controlled by varying the substituents on
give
tetranuclear
complexes
[(RnSnX3−
* Corresponding author. Tel.: +86-22-2350-4446; fax: +86-22-
2350-2458.
E-mail address: tanglf311@263.net (L.-F. Tang).
n)(CO)3MꢀC5H4C(O)CH2]2 (M=Mo or W; R=Ph or
Me; X=Cl or Br; n=2 or 3).
0277-5387/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0277-5387(00)00647-1

404
L.-F. Tang et al. / Polyhedron 20 (2001) 403–408
2. Experimental
obtained when the dianion was reacted with Ph2SnCl2
in a 1:1 ratio.
All reactions were carried out under an argon atmo-
sphere using standard Schlenk and cannula techniques.
Diglyme, hexane and THF were distilled from sodium
and benzophenone ketyl prior to use. Element analyses
were carried out on a Perkin–Elmer 240C analyzer.
The 1H NMR spectra were obtained with a Bruker
AC-P 200 MHz spectrometer using CDCl3 as solvent
unless otherwise noted. The chemical shifts were re-
ported in ppm with respect to the references. IR spectra
data were obtained from a Nicolet FT-IR 170SX spec-
trometer using KBr discs. 1,4-Bis(cyclopentadienyl
sodium)-1,4-butadione was prepared by published
method [13].
2.4. Preparation of
[(Ph2SnBr)(CO)3MoC5H4C(O)CH2]2 (3)
Compound 3 was obtained similarly using Ph2SnBr2
to react with the dianion as described above for 1. After
a similar workup, yellow crystals of 3 were obtained.
Yield: 32%. Anal. Found: C, 40.85; H, 2.51. Calc. for
C44H32Br2Mo2O8Sn2: C, 41.34; H, 2.50%. H NMR: l
7.64 (m, 8H); 7.38 (m, 12H); 5.93 (t, 4H); 5.46 (t, 4H);
1
2.85 (s, 4H) ppm. IR: w (CO) 2021.7 (s), 1962.9 (s),
1919.5 (vs); w (ketone CO) 1692.1 (m) cm−1
.
2.1. Preparation of [Na(CO)3MoC5H4C(O)CH2]2
2.5. Preparation of
[(Me2SnCl)(CO)3MoC5H4C(O)CH2]2 (4)
1,4-Bis(cyclopentadienylsodium)-1,4-butadione (0.28
g, 1.1 mmol) was added to a solution of Mo(CO)6 (0.26
g, 1.0 mmol) in 20 ml of THF. The mixture was stirred
and refluxed for 20 h to obtain a blue black solution of
[Na(CO)3MoC5H4C(O)CH2]2. After cooling to room
temperature, the solution was ready for subsequent use.
Compound 4 was obtained similarly using Me2SnCl2
to react with the dianion as described above for 1. After
a similar workup, yellow crystals of 4 were obtained.
Yield: 34%. Anal. Found: C, 29.51; H, 2.36. Calc. for
C24H24Cl2Mo2O8Sn2·CH2Cl2: C, 29.23; H, 2.53%. 1H
NMR: l 5.97 (t, 4H); 5.49 (t, 4H); 2.98 (s, 4H); 0.95 (s,
12H) ppm. IR: w (CO) 2003.5 (s), 1974.5 (s), 1928.4 (vs);
2.2. Preparation of [(Ph3Sn)(CO)3MoC5H4C(O)CH2]2
(1)
w (ketone CO) 1686.1 (m) cm−1
.
To the above solution of [Na(CO)3MoC5H4C
(O)CH2]2 in THF, Ph3SnCl (0.77 g, 2.0 mmol) was
added and stirred overnight at room temperature. The
solvent was removed under reduced pressure and the
residue was extracted with CH2Cl2. The extracted solu-
tion was passed through a short neutral alumina
column eluted with CH2Cl2 to obtain a yellow solution.
After removing the solvent, the residue was recrystal-
lized from CH2Cl2–hexane to yield yellow crystals of 1.
Yield: 38%. Anal. Found: C, 51.95; H, 3.48. Calc. for
C56H42Mo2O8Sn2·1/2CH2Cl2: C, 51.58; H, 3.27%. 1H
NMR: l 7.52 (m, 12H); 7.34 (m, 18H); 5.77 (t, 4H);
5.32 (t, 4H); 2.78 (s, 4H) ppm. IR: w (CO) 2001.4 (vs),
1935.8 (sh), 1892.4 (vs); w (ketone CO) 1690.2 (m)
2.6. Preparation of [Na(CO)3WC5H4C(O)CH2]2
1,4-Bis(cyclopentadienylsodium)-1,4-butadione (0.28
g, 1.1 mmol) was added to a solution of W(CO)6 ( 0.35
g, 1.0 mmol) in 20 ml of diglyme. The mixture was
stirred and refluxed for 6 h to obtain a blue–black
solution of [Na(CO)3WC5H4C(O)CH2]2. After cooling
to room temperature, the solution was ready for subse-
quent use.
2.7. Preparation of [(Ph3Sn)(CO)3WC5H4C(O)CH2]2
(5)
cm−1
.
Ph3SnCl (0.77 g, 2.0 mmol) was added to the above
solution of [Na(CO)3WC5H4C(O)CH2]2 in diglyme, and
the mixture was stirred overnight at room temperature.
Water (30 ml) was added to the mixture to precipitate
out a black solid. After filtering and drying, the solid
was dissolved in CH2Cl2 and passed through a short
neutral alumina column eluted with CH2Cl2 to obtain a
yellow solution. After removing the solvent, the residue
was recrystallized from CH2Cl2–hexane to yield yellow
crystals of 5. Yield: 45%. Anal. Found: C, 45.27; H,
2.96. Calc. for C56H42O8Sn2W2·3H2O: C, 44.74; H,
2.3. Preparation of [(Ph2SnCl)(CO)3MoC5H4C(O)CH2]2
(2)
Compound 2 was obtained similarly using Ph2SnCl2
instead of Ph3SnCl to react with the dianion. After a
similar workup as employed for the isolation of 1,
yellow crystals of 2 were obtained. Yield: 43%. Anal.
Found: C, 41.24; H, 2.61. Calc. for C44H32Cl2Mo2-
O8Sn2·3/2CH2Cl2: C, 41.47; H, 2.65%. 1H NMR: l
7.64–7.38 (m, 20H); 5.97 (t, 4H); 5.57 (t, 4H); 2.86 (s,
4H) ppm. IR: w (CO) 1996.8 (s), 1925.8 (m), 1898.2 (s);
w (ketone CO) 1657.2 (m) cm−1. The same product was
1
3.20%. H NMR: l 7.48–7.33 (m, 30H); 5.80 (t, 4H);
5.42 (t, 4H); 2.77 (s, 4H) ppm. IR: w (CO) 2006.9 (vs),
1943.9 (s), 1893.1 (vs); w (ketone CO) 1688.1(m) cm−1
.

L.-F. Tang et al. / Polyhedron 20 (2001) 403–408
405
2.8. Preparation of [(Ph2SnCl)(CO)3WC5H4C(O)CH2]2
(6)
Dry HCl gas was continuously bubbled into the solu-
tion, the color of the solution slowly turned from light
yellow to orange. After 30 min, the solvent was re-
moved and the residue was recrystallized from
CH2Cl2–hexane to afford yellow crystals of 9. Yield:
88%. Anal. Found: C, 23.23; H, 1.61. Calc. for
Compound 6 was obtained by a similar method as
described for 5. Yield: 45%. Anal. Found: C, 37.34; H,
2.42. Calc. for C44H32Cl2O8Sn2W2·CH2Cl2: C, 37.24; H,
1
1
2.34%. H NMR: l 7.53–7.38 (m, 20H); 5.97 (t, 4H);
C20H12Cl6Mo2O8Sn2: C, 23.46; H, 1.17%. H NMR: l
5.57 (t, 4H); 2.86 (s, 4H) ppm. IR: w (CO) 1993.2 (s),
6.13 (t, 4H); 5.76 (t, 4H); 3.00 (s, 4H) ppm. IR: w (CO)
2046.6 (vs), 1966.5 (s), 1940.7 (s); w (ketone CO) 1692.8
1891.8 (vs, br); w (ketone CO) 1652.8 (m) cm−1
.
(m) cm−1
.
2.9. Preparation of [(Ph2SnBr)(CO)3WC5H4C(O)CH2]2
(7)
2.12. Preparation of [(SnCl3)(CO)3WC5H4C(O)CH2]2
(10)
Compound 7 was obtained by a similar method as
described for 5. Yield: 38%. Anal. Found: C, 36.45; H,
2.42. Calc. for C44H32Br2O8Sn2W2: C, 36.31; H, 2.20%.
1H NMR: l 7.65 (m, 8H); 7.41 (m, 12H); 5.97 (t, 4H);
5.57 (t, 4H); 2.85 (s, 4H) ppm. IR: w ( CO) 2017.4 (s),
This compound was obtained by a similar method as
described for 9. Yield: 90%. Anal. Found: C, 20.32; H,
1.35. Calc. for C20H12Cl6O8Sn2W2: C, 20.02; H, 1.00%.
1H NMR: l 6.12 (t, 4H); 5.75 (t, 4H); 3.00 (s, 4H) ppm.
IR: w (CO) 2044.5 (s), 1967.5 (s), 1940.4 (s); w (ketone
1955.3 (s), 1905.2 (vs); w (ketone CO) 1692.5 (m) cm−1
.
CO) 1693.1 (m) cm−1
.
2.10. Preparation of
[(Me2SnCl)(CO)3WC5H4C(O)CH2]2 (8)
2.13. X-ray crystallography
Compound 8 was obtained by a similar method as
described for 5. Yield: 36%. Anal. Found: C, 24.98; H,
2.10. Calc. for C24H24Cl2O8Sn2W2·CH2Cl2: C, 24.95; H,
Crystals of 4 and 5 suitable for X-ray analysis were
obtained from a CH2Cl2–hexane solution at −10°C.
Intensity data were collected on a Bruker SMART
diffractometer with graphite monochromated Mo Ka
1
2.16%. H NMR: l 6.01 (t, 4H); 5.60 (t, 4H); 2.98 (s,
,
4H), 0.95 (s, 12H) ppm. IR: w (CO) 2000.8 (s), 1973.5
radiation (u=0.71073 A) at 25°C to a maximum 2q
(s), 1895.7 (s); w (ketone CO) 1678.7 (m) cm−1
.
value of 50°. An empirical absorption correction was
applied to intensity data. The structure was solved by
direct methods and refined by full-matrix least-squares.
The non-hydrogen atoms were refined anisotropically.
The data collection and refinement parameters are sum-
marized in Table 1.
2.11. Preparation of [(SnCl3)(CO)3MoC5H4C(O)CH2]2
(9)
Compound 1 (0.64 g, 0.5 mmol) was dissolved in 20
ml of CH2Cl2 and the solution was cooled to −15°C.
3. Results and discussion
Table 1
Crystal data for 4 and 5
3.1. Synthesis and properties of complexes
Compound
4·CH2Cl2
5·3H2O
Using the convenient salt elimination method, we
have previously carried out the reaction of the anion of
tricarbonyl cyclopentadienyl (or methylcyclopentadi-
enyl) tungsten with diorganotin(IV) halides to afford
WꢀSnꢀW bonded trimetallic complexes. It was difficult
to control the stepwise replacement of tin halide to
form bimetallic complexes [14]. However, the reaction
of the anion of tricarbonyl formyl [15] or acetylcy-
clopentadienyl [12] tungsten (molybdenum) with
diorganotin(IV) halides only yielded SnꢀM bonded
bimetallic complexes, even with an excess of metal
anions. In the present work, analogous results were
Formula
Mr
Crystal size (mm)
Crystal system
Space group
Cell parameters
C25H26Cl4Mo2O8Sn2 C56H48O11Sn2W2
1025.52
1502.02
0.10×0.25×0.30
monoclinic
C2/c
0.20×0.25×0.30
monoclinic
C2/c
,
a (A)
37.712(3)
7.1073(6)
13.148(1)
103.327(2)
3429.1(5)
4
21.055(2)
19.761(2)
15.924(2)
114.580(2)
6024.9(12)
4
,
b (A)
,
c (A)
i (°)
3
,
V (A )
Z
Reflections measured
Reflections observed
Parameters
Goodness-of-fit
Residuals R, Rw
6866
12481
3038 [I]2|(I)]
189
4016 [I]2|(I)]
330
obtained.
The
reactions
of
the
dianions
[(CO)3MC5H4C(O)CH2]22− with organotin(IV) halides
yielded tetranuclear complexes 1–8 in reasonable yield,
and only one halide atom of diorganotin dihalide was
1.026
1.088
0.023, 0.057
0.035, 0.12

406
L.-F. Tang et al. / Polyhedron 20 (2001) 403–408
Reactions of complexes 1 and 5 with dry HCl in cool
CH2Cl2 solution gave complexes 9 and 10 in good
yields, respectively, which indicates that the metal–
metal bonds in complexes 1 and 5 are stable (Scheme
2). All solid complexes are stable in air, and they are
soluble in chlorinated solvents. There are six metal
carbonyls and two ketone carbonyls in complexes 1–8,
but their IR spectra only show three typical metal
carbonyl stretching bands in the range of 2020–1890
cm−1 and one absorption band of ketone carbonyl on
the cyclopentadienyl ring between 1652 and 1692 cm−1
.
These data show that the complexes may be symmetri-
cal, which is consistent with the results of X-ray crystal
structures of complexes 4 and 5. A significant shift
toward higher wave numbers for the metal carbonyls in
complexes 9 and 10 is observed, compared with those in
complexes 1 and 5. This may be attributed to the
electron-withdrawing effect of chlorine strengthening
the d–d interactions of SnꢀMo and SnꢀW, in turn
weakening metal–carbonyl back bonding. The 1H
NMR spectra exhibit the expected proton signals and
two equivalent cyclopentadienyl rings. The Cp ring
resonances are observed as two triplets which are sepa-
rated by ca. 0.4 ppm in all complexes. However, a
downfield shift trend of cyclopentadienyl protons with
an increased number of halide ligands is observed. This
may be attributed to the influence of an electron-with-
drawing effect of the halide through a p-bonding inter-
action [17].
Scheme 1.
3.2. Crystal structures of complexes 4 and 5
Scheme 2.
The C2 molecular structure of 4 is presented in Fig. 1.
Selected bond lengths and angles are shown in Table 2.
There is one solvated CH2Cl2 molecule in the crystal.
The molybdenum center adopts a 3:4 piano four-legged
square pyramid structure, as calculated by Kubacek for
CpML4 complexes [18]. Two SnꢀMo units are linked by
the (h5-C5H4COCH2)2 ligand and are located in a mu-
tually trans position. The SnꢀMo bond distance is
replaced even with an excess of dianion (Scheme 1). No
polymeric {[(Ph2Sn)(CO)3MC5H4C(O)CH2]2}n or cyclic
{[(CO)3MC5H4C(O)CH2]2SnPh2} products were ob-
tained [16], indicating that the electron-withdrawing
groups on cyclopentadienyl rings significantly decrease
the
anions.
nucleophilicity
of
cyclopentadienyl
metal
,
2.7755(3) A, considerably shorter than the sum of
,
covalent radii (1.39+1.61 A), which indicates partial
Fig. 1. Molecular structure of complex 4. The thermal ellipsoids are drawn at the 30% probability level.

L.-F. Tang et al. / Polyhedron 20 (2001) 403–408
407
Table 2
Selected bond lengths (A) and angles (°) for 4
Table 3
,
,
Selected bond lengths (A) and angles (°) for 5
Mo(1)ꢀC(2)
Mo(1)ꢀC(1)
Mo(1)ꢀC(3)
Mo(1)ꢀC(5)
Mo(1)ꢀC(6)
Mo(1)ꢀC(9)
Mo(1)ꢀC(7)
Mo(1)ꢀC(8)
Mo(1)ꢀSn(1)
Sn(1)ꢀC(12)
1.972(4)
1.981(4)
2.003(4)
2.291(3)
2.311(3)
2.320(3)
2.343(3)
2.357(3)
2.7755(4)
2.115(4)
C(1)ꢀO(1)
C(2)ꢀO(2)
C(3)ꢀO(3)
C(4)ꢀO(4)
C(4)ꢀC(5)
C(4)ꢀC(10)
Sn(1)ꢀCl(1)
Cl(2)ꢀC(13)
Sn(1)ꢀC(11)
1.145(4)
1.139(4)
1.125(4)
1.205(4)
1.481(5)
1.491(5)
2.399(1)
1.743(5)
2.131(4)
Sn(1)ꢀC(11)
Sn(1)ꢀC(23)
Sn(1)ꢀC(17)
Sn(1)ꢀW(1)
W(1)ꢀC(3)
W(1)ꢀC(1)
W(1)ꢀC(2)
W(1)ꢀC(6)
W(1)ꢀC(7)
2.150(9)
2.16(1)
2.167(9)
2.8154(7)
1.964(9)
1.97(1)
1.99(1)
2.298(8)
2.313(8)
W(1)ꢀC(10)
W(1)ꢀC(9)
O(1)ꢀC(1)
O(2)ꢀC(2)
O(3)ꢀC(3)
O(4)ꢀC(5)
C(4)ꢀC(5)
C(5)ꢀC(6)
W(1)ꢀC(8)
2.349(8)
2.373(9)
1.16(1)
1.14(1)
1.16(1)
1.20(1)
1.49(1)
1.48(1)
2.320(9)
C(11)ꢀSn(1)ꢀC(23) 104.5(4)
C(11)ꢀSn(1)ꢀC(17) 110.0(3)
C(23)ꢀSn(1)ꢀC(17) 104.2(4)
C(11)ꢀSn(1)ꢀW(1) 115.9(2)
C(23)ꢀSn(1)ꢀW(1) 109.4(3)
C(17)ꢀSn(1)ꢀW(1) 111.9(3)
C(3)ꢀW(1)ꢀC(1)
C(3)ꢀW(1)ꢀC(2)
C(1)ꢀW(1)ꢀC(2)
O(4)ꢀC(5)ꢀC(6)
O(4)ꢀC(5)ꢀC(4)
C(6)ꢀC(5)ꢀC(4)
C(10)ꢀC(6)ꢀC(5)
C(7)ꢀC(6)ꢀC(5)
C(16)ꢀC(11)ꢀSn(1) 119.0(8)
C(12)ꢀC(11)ꢀSn(1) 122.9(7)
C(3)ꢀW(1)ꢀSn(1)
C(1)ꢀW(1)ꢀSn(1)
C(2)ꢀW(1)ꢀSn(1)
C(18)ꢀC(17)ꢀSn(1) 126.1(8)
C(22)ꢀC(17)ꢀSn(1) 117.5(8)
C(28)ꢀC(23)ꢀSn(1) 121.5(8)
119.7(9)
122.0(9)
118.1(8)
127.2(9)
124.4(9)
C(2)ꢀMo(1)ꢀC(1)
C(2)ꢀMo(1)ꢀC(3)
C(1)ꢀMo(1)ꢀC(3)
C(2)ꢀMo(1)ꢀSn(1)
C(1)ꢀMo(1)ꢀSn(1)
C(3)ꢀMo(1)ꢀSn(1) 131.4(1)
C(5)ꢀMo(1)ꢀSn(1) 131.74(8)
O(4)ꢀC(4)ꢀC(10)
C(5)ꢀC(4)ꢀC(10)
C(9)ꢀC(5)ꢀC(4)
C(6)ꢀC(5)ꢀC(4)
105.9(1)
78.8(1)
80.4(1)
71.62(9)
72.1(1)
C(12)ꢀSn(1)ꢀC(11) 112.2(2)
C(12)ꢀSn(1)ꢀCl(1)
C(11)ꢀSn(1)ꢀCl(1)
C(12)ꢀSn(1)ꢀMo(1) 120.1(1)
C(11)ꢀSn(1)ꢀMo(1) 113.7(1)
Cl(1)ꢀSn(1)ꢀMo(1) 104.22(3)
O(1)ꢀC(1)ꢀMo(1)
O(2)ꢀC(2)ꢀMo(1)
O(3)ꢀC(3)ꢀMo(1)
O(4)ꢀC(4)ꢀC(5)
102.1(2)
101.6(1)
106.6(4)
78.3(4)
79.5(4)
176.9(3)
175.9(3)
177.1(3)
120.1(3)
72.9(3)
72.2(3)
131.1(3)
122.3(3)
117.5(3)
128.1(3)
124.4(3)
C(24)ꢀC(23)ꢀSn(1) 119.9(8)
O(1)ꢀC(1)ꢀW(1)
O(2)ꢀC(2)ꢀW(1)
O(3)ꢀC(3)ꢀW(1)
175.5(8)
177.7(9)
176.6(8)
multiple bond character in the SnꢀMo metalꢀmetal
bond (little p-bonding interactions between Sn and Mo)
[19]. This bond distance is similar to that in the non-
bridged acetylcyclopentadienyl complex CH3COC5H4-
but longer than the SnꢀMo bond in complex 4, for W
and Mo have similar covalent radii. The configuration
of the tin atom is analogous to that in complex 4,
namely a distorted tetrahedral geometry.
,
Mo(CO)3SnPh2Cl (2.7683(6) A) [12], but longer than
that in 2,4-(NO2)2C6H3NHNꢁC(CH3)C5H4Mo-
,
(CO)3SnCl3 (2.7040(7) A) [20]. The tin atom is a dis-
torted tetrahedral geometry with SnꢀC(11), SnꢀC(12)
and SnꢀCl(1) bond lengths of 2.131(4), 2.115(4) and
4. Supplementary material
Atomic coordinates, thermal parameters and bond
lengths and angles for complexes 4 and 5 have been
deposited at the Cambridge Crystallographic Data Cen-
tre, CCDC nos. 146944 and 146945. Copies of this
information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge, CB2
1EZ, UK (fax: +44-1223-336-033; e-mail: de-
posit@ccdc.cam.ac.uk or www: http://www.ccdc.
cam.ac.uk).
,
2.399(1) A, respectively.
The molecular structure of 5 is shown in Fig. 2.
Selected bond lengths and angles are shown in Table 3.
There are three lattice water molecules in the crystal.
The configuration of the tungsten atom is analogous to
that of molybdenum atom in complex 4. The SnꢀW
,
bond length is 2.8154(7) A, which is slightly shorter
,
than that in CH3C5H4W(CO)3SnPh3 (2.8322(4) A) [14],
Fig. 2. Molecular structure of complex 5. The thermal ellipsoids are drawn at the 30% probability level.

408
L.-F. Tang et al. / Polyhedron 20 (2001) 403–408
[9] L. Verdonck, A.R. Bossuyt, A. Praet, F. Verpoort, J. Geeraert,
Acknowledgements
D. Van de Vondel, P. Van der Kelen, J. Mol. Catal. 76 (1992)
319.
This work is supported by the National Natural
Science Foundation of China and the State Key Labo-
ratory of Elemento-Organic Institute of Nankai Uni-
versity.
[10] L.F. Tang, Z.H. Wang, J.T. Wang, Chem. J. Chin. Univ. 20
(1999) 577.
[11] L.F. Tang, Z.H. Wang, Y.M. Xu, J.T. Wang, H.G. Wang, X.K.
Yao, Polyhedron 17 (1998) 3765.
[12] J.T. Wang, H.Y. He, Y.M. Xu, J. Sun, X.F. Kong, Heteroatom
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[13] T.E. Bitterwolf, J. Organomet. Chem. 386 (1990) 9.
[14] H.Y. He, J.T. Wang, Y.M. Xu, Chem. Res. Chin. Univ. 13
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