21.4 Hz, PCSn), 175.4 (d, (1 + 2)JPC 3.1 Hz, PCO), 197.2 (d, 2JPC 8.5 Hz, cis-
CO), 198.7 (d, 2JPC 28.5 Hz, trans-CO); 31P NMR, d 298.2 (s, h1/2 95 Hz);
MS (EI, 120Sn, 184W): M+ at m/z = 934.
6c (6a,b: C3: (1 + 2)JPC 25 ± 3 Hz, C2: (1 + 2)JPC @ 3 Hz; 6c: 4.9
and 2.0 Hz8).
The X-ray crystal structure analysis of the complex 6b
confirms the molecular structure (Fig. 1).§ In comparison to the
structure 8 of 6c (values given in square brackets) the endocyclic
P–C bond lengths of 6b are lengthened {P(1)–C(6) 1.828(4)
[1.792(8)], P(1)–C(7) 1.768(4) [1.753(8)], C(6)–C(7) 1.323(6)
[1.298(11)] Å}, probably because of increased steric strain in
6b.
§ Crystal data for 6b: C34H39O6PSi2SnW, monoclinic, space group P21/c,
a = 21.024(2), b = 9.2419(10), c = 19.619(3) Å, b = 95.753(15)°, U =
3792.8(8) Å3, Z = 4, m = 3.8 mm21, T = 2130 °C. Colourless block 0.6
3 0.5 3 0.5 mm, Mo-Ka radiation, Stoe STADI-4 diffractometer, 8387
intensities to 2qmax 50°, 6681 unique (Rint 0.021) used for all calculations.
Structure solution by heavy-atom method, anisotropic refinement on F2
(program SHELXL-97, G. M. Sheldrick, Univ. of Go¨ttingen). Treatment of
H atoms: rigid methyls, others riding. Final wR(F2) 0.075, conventional
R(F) 0.030 for 412 parameters. CCDC 182/930.
We are currently investigating the synthetic potential of this
1
new route to h -1-phosphaallene complexes and the reactivity
of the complexes 5a,b and 6a,b.
This work was supported by the Fonds der Chemischen
Industrie and by the Deutsche Forschungsgemeinschaft. We
thank Mr A. Weinkauf for X-ray data collection.
1 Review: R. Appel, in Multiple Bonds and Low Coordination in
Phosphorus Chemistry, ed. M. Regitz and H. J. Scherer, Georg Thieme
Verlag, Stuttgart, New York, 1990, p. 157.
2 Reviews: F. Mathey, Chem. Rev., 1990, 90, 997; F. Mathey and M.
Regitz, in Comprehensive Heterocyclic Chemistry II, ed. A. R. Katritzky,
C. W. Rees and E. F. V. Scriven, Pergamon, New York, 1997, p. 277.
3 R. Appel, F. Knoch and V. Winkhaus, J. Organomet. Chem., 1986, 307,
93.
4 M. A. Kirms, H. Primke, M. Stohlmeier and A. de Meijere, Recl. Trav.
Chim. Pays-Bas, 1986, 105, 462.
5 R. Streubel, A. Ostrowski, S. Priemer, U. Rohde, J. Jeske and P. G. Jones,
Eur. J. Inorg. Chem., 1998, 257.
6 S. V. Ponomarev, S. Y. Pechurina and I. F. Lutsenko, Zh. Obschch.
Khim., 1969, 39, 1171; S. V. Ponomarev, M. B. Erman, S. A. Lebedev,
S. Y. Pechurina and I. F. Lutsenko, Zh. Obshch. Khim., 1971, 41, 127.
7 R. Streubel and H. Wilkens, unpublished work.
8 A. Ostrowski, J. Jeske, P. G. Jones and R. Streubel, J. Chem. Soc., Chem.
Commun., 1995, 2507; A. Ostrowski, J. Jeske, F. Ruthe, P. G. Jones and
R. Streubel, Z. Anorg. Allg. Chem., 1997, 623, 1897.
Notes and References
† E-mail: r.streubel@tu-bs.de
‡ Correct elemental analysis were obtained for complexes 5b and 6b. NMR
data were recorded at room temperature in CDCl3 solution at 50.3 MHz
(
13C) and 81.0 MHz (31P); J/Hz. Selected spectroscopic data for 5a: 13C
1
1
NMR, d 28.3 (s, J119
356.3, J117
339.3, Hz, SnMe3), 156.1 (s,
PNCNC), 196.4 (d, 2JPC 9.7 Hz, cis-CO), S2n0C0.2 (d, 2JPC 30.3 Hz, trans-CO),
SnC
226.5 (d, 1JPC 90.9 Hz, PNCNC); 31P NMR, d 76.4 (s, 1JWP 262.6, 3J119
SnP
152.8, 3J117SnP 144.3 Hz). 5b: 13C NMR, d 154.5 (d, 2JPC 2.0 Hz, PNCNC),
196.2 (d, 2JPC 9.2 Hz, cis-CO), 199.8 (d, 2JPC 30.4 Hz, trans-CO), 227.8 (d,
1JPC 90.4 Hz, PNCNC); 31P NMR, d 87.4 (s, JWP 265.5, J119
174.7,
1
3
SnP
3J117SnP 167.5 Hz). 6a: 13C NMR, d 26.8 (s, 1J119SnC 371.4, 1J117SnC 355.1
(1 + 2)
2
Hz, SnMe3), 97.2 (d,
J
23.2 Hz, PCSn), 172.5 (s, JSnC 53.4 Hz,
PC
PCO), 197.6 (d, 2JPC 8.2, 1JWC 126.4 Hz, cis-CO), 199.8 (d, 2JWC 29.3 Hz,
trans-CO); 31P NMR, d 2107.4 (s, h1/2 15 Hz, 1JWP 265.1, 2JSnP 49.6 Hz);
MS (EI, 120Sn, 184W): M+ at m/z = 934. 6b: 13C NMR, d 94.7 (d, (1 + 2)JPC
Received in Basel, Switzerland, 9th June 1998; 8/04385J
1762
Chem. Commun., 1998