(200 mg, 0.364 mmol) in thf (30 cm3) was added HSPh (0.037 cm3,
0.364 mmol) and NEt3 (0.050 cm3, 0.364 mmol). The solution,
which became dark blue after 30 min, was stirred for 1 h and
then the mixture was evaporated to dryness in vacuo. The residue
was extracted with diethyl ether (30 cm3) and the extract filtered
The solvent was then removed and the blue residue dissolved in the
minimum volume of CH2Cl2 (ca. 3 cm3) and placed on an alumina–
n-hexane chromatography column. Elution with n-hexane–diethyl
ether (1 : 4) gave a blue band which was collected and evaporated to
dryness in vacuo. Crystallisation from n-hexane at -78 ◦C gave blue
Crystal structure determinations of [Mo(SMe)(CO)(g-MeC
≡
≡
CMe)(g-C5H5)] 1, [Mo(SMe)(CO)(g-PhC CPh)(g-C5H5)] 3,
≡
[Mo(SPh)(CO)(g-PhC CPh)(g-C5H5)] 4, [Mo(SMe){P-
≡
(OMe)3}(g-MeC CMe)(g-C5H5)] 7, [Mo(SPh){P(OMe)3}(g-
≡
≡
MeC CMe)(g-C5H5)] 8, [W(SPh){P(OMe)3}(g-MeC CMe)-
≡
(g-C5H5)] 11, [W(SMe)(CO)(g-PhC CPh)Tp¢] 12,
[W(SPh)(CO)(g-PhC CPh)Tp¢] 13 and [W(SPh)-
≡
+
-
≡
(CO)(g-PhC CPh)Tp¢][PF6] 13 [PF6]
≡
Crystals of [Mo(SMe)(CO)(h-MeC CMe)(h-C5H5)] 1, [Mo-
≡
≡
(SMe)(CO)(h-PhC CPh)(h-C5H5)] 3, [Mo(SPh)(CO)(h-PhC
≡
needles of [Mo(SPh){P(OMe)3}(h-MeC CMe)(h-C5H5)], yield
≡
[Mo(SMe){P(OMe)3}(h-MeC CMe)(h-
CPh)(h-C5H5)]
4,
117 mg (72%).
≡
C5H5)] 7, [Mo(SPh){P(OMe)3}(h-MeC CMe)(h-C5H5)] 8,
≡
[Mo(SMe){P(OMe)3}(h-MeC CMe)(h-
The
complexes
≡
[W(SPh){P(OMe)3}(h-MeC CMe)(h-C5H5)] 11, [W(SMe)(CO)-
≡
C5H5)] 7, [Mo(SMe){P(OMe)3}(h-PhC CPh)(h-C5H5)] 9 and
≡
≡
(h-PhC CPh)Tp¢] 12, [W(SPh)(CO)(h-PhC CPh)Tp¢] 13 and
≡
[Mo(SPh){P(OMe)3}(h-PhC CPh)(h-C5H5)] 10 were prepared
+
-
≡
[W(SPh)(CO)(h-PhC CPh)Tp¢][PF6] 13 [PF6] were grown at
-20 ◦C by allowing n-hexane to diffuse into a concentrated
solution of the complex in CH2Cl2.
similarly.
≡
Many of the details of the structure analyses of 1, 3, 4, 7, 8,
11–13 and 13+[PF6]- are listed in Table 5. Diffraction intensities
were collected on a Bruker SMART CCD diffractometer, with
[W(SPh){P(OMe)3}(g-MeC CMe)(g-C5H5)] 11. To a stirred
≡
suspension of [W{P(OMe)3}2(h-MeC CMe)(h-C5H5)][BF4]
(176 mg, 0.256 mmol) in thf (30 cm3) was added HSPh (0.027 cm3,
0.253 mmol) and NEt3 (0.035 cm3, 0.253 mmol). The reaction
mixture, which became pink after 20 min, was stirred for 2 h
and then evaporated to dryness in vacuo. The pink residue was
extracted with diethyl ether (30 cm3) and the extract filtered. The
filtrate was then evaporated to dryness in vacuo and the resulting
pink residue dissolved in the minimum volume of CH2Cl2 (ca.
3 cm3) and placed on an alumina–n-hexane chromatography
column. Elution with n-hexane–diethyl ether (1 : 1) gave a
pink solution which was collected and evaporated to dryness
in vacuo. Crystallisation from diethyl ether at -78 ◦C gave
˚
graphite-monochromated Mo-Ka (0.71073 A) radiation, and
corrected for absorption using SADABS.26 The structures were
solved by SHELXS-97, expanded by Fourier-difference syntheses,
and refined with the SHELXL-97 package incorporated into the
SHELXTL crystallographic package.27 The positions of the hydro-
gen atoms were calculated by assuming ideal geometries but were
not refined. All non-hydrogen atoms were refined with anisotropic
thermal parameters by full-matrix least-squares procedures on
F2. The structure of 13 has two crystallographically independent
molecules within the asymmetric unit, designated 13A and 13B
in Table 4. The solution of this structure revealed many small
electron-density peaks which could not be satisfactorily modelled,
and the data were therefore treated with the PLATON SQUEEZE
≡
[W(SPh){P(OMe)3}(h-MeC CMe)(h-C5H5)] as a pink solid,
yield 93 mg (66%).
routine.28 This calculated that each unit cell contained four voids
≡
[W(SMe)(CO)(g-PhC CPh)Tp¢] 12. To a stirred solution of
[W(CO)2(h-PhC CPh)Tp¢][BF4] (580 mg, 0.723 mmol) in thf
3
˚
of 411 A , each holding about 90 electrons (which may correspond
≡
to two badly disordered dichloromethane molecules).
CCDC reference numbers 738814–738822. For crystallographic
data in CIF or other electronic format see DOI: 10.1039/b912986c
(120 cm3) was added NaSMe (61 mg, 0.868 mmol). After 3 h,
the green solution was evaporated to dryness in vacuo. The green
residue was redissolved in diethyl ether (50 cm3) and filtered, silica
was added to the solution and then the mixture was dried in vacuo.
The residue was placed on a silica–n-hexane chromatography
column. Elution with n-hexane–diethyl ether (10 : 1) gave a green
band which was collected and evaporated to dryness in vacuo.
Purification using CH2Cl2–n-hexane gave the product as a green
solid, yield 97 mg (18%).
Acknowledgements
We thank the University of Bristol (E.P.), the EPSRC (A.B.) and
the Royal Thai Government (S.B. and A.K.) for Postgraduate
Scholarships.
≡
The complex [W(SPh)(CO)(h-PhC CPh)Tp¢] 13 was prepared
similarly.
References
1 C. J. Adams, I. M. Bartlett, S. Boonyuen, N. G. Connelly, D. J. Harding,
O. D. Hayward, E. J. L. McInnes, A. G. Orpen, M. J. Quayle and P. H.
Rieger, Dalton Trans., 2006, 3466.
2 C. J. Adams, I. M. Bartlett, S. Carlton, N. G. Connelly, D. J. Harding,
O. D. Hayward, A. G. Orpen, E. Patro´n, C. D. Ray and P. H. Rieger,
Dalton Trans., 2007, 62.
3 C. J. Adams, K. M. Anderson, N. G. Connelly, D. J. Harding, O. D.
Hayward, A. G. Orpen, E. Patro´n and P. H. Rieger, Dalton Trans.,
2009, 530.
4 P. S. Braterman, J. L. Davidson and D. W. A. Sharp, J. Chem. Soc.,
Dalton Trans., 1976, 241.
5 J. A. K. Howard, R. F. D. Stansfield and P. Woodward, J. Chem. Soc.,
Dalton Trans., 1976, 246.
+
-
≡
[W(SMe)(CO)(g-PhC CPh)Tp¢][BF4] 12 [BF4] . To a stirred
≡
solution of [W(SMe)(CO)(h-PhC CPh)Tp¢] (84 mg, 0.114 mmol)
in CH2Cl2 (25 cm3) was added [Fe(h-C5H4COMe)(h-C5H5)][BF4]
(35 mg, 0.112 mmol). After 10 min, the green solution was filtered,
n-hexane (50 cm3) was added, and the volume of the solution
reduced in vacuo, inducing precipitation of a dark-green solid
which was washed with n-hexane (2 ¥ 10 cm3) and diethyl ether
(3 ¥ 10 cm3), yield 61 mg (65%).
+
-
≡
The complex [W(SPh)(CO)(h-PhC CPh)Tp¢][BF4] 13 [BF4]
was prepared similarly.
This journal is
The Royal Society of Chemistry 2009
Dalton Trans., 2009, 9746–9758 | 9757
©