Molecular Bismuth Phosphorus Compounds Containing Bi2 Units
1588 (w), 1567 (w), 1486 (w), 1470 (m), 1426 (s), 1389 (m), 1359
FULL PAPER
ppm. 31P{1H} NMR ([D8]toluol, –50 °C): –82.3 (m), –102.0 (m),
(m), 1309 (w), 1262 (w), 1188 (m), 1157 (w), 1102 (vs), 1028 (w), –145.1 (m), –279.5 (m) ppm. IR (KBr): ν 3132 (w), 3068 (m), 3046
˜
1007 (m), 934 (m), 846 (w), 816 (s), 740 (s), 698 (vs), 620 (w), 597
(m), 3013 (w), 2959 (s), 2925 (s), 2889 (m), 2854 (s), 1955 (w), 1890
(w), 1822 (w), 1719 (w), 1586 (w), 1565 (w), 1484 (w), 1468 (m),
1426 (s), 1389 (m), 1361 (m) 1303 (w), 1262 (m), 1192 (w), 1156
(vw), 1100 (vs), 1008 (m), 936 (w), 853 (w) 814 (s), 737 (s), 699 (vs),
620 (w), 595 (m), 516 (vs), 484 (s), 405 (m) cm–1.
(s), 561 (w), 518 (vs), 483 (s), 454 (s), 402 (m) cm–1.
1 and 2: Butyllithium solution (0.37 mL, 1.6 ) was added to a
solution of (tBuPh2Si)2PH (0.3 g, 0.59 mmol) in Et2O (10 mL) at
0 °C. After warming to room temperature, the solution of
(tBuPh2Si)2PLi was added to a suspension of 0.06 g (0.2 mmol)
BiCl3 in 10 mL Et2O at –60 °C. Subsequently the red mixture was
slowly warmed to room temperature while stirring and then agi-
tated overnight. The solution was reduced to 5 mL in vacuo. After
filtration and cooling to 0 °C red crystals of 1 were obtained within
a few hours. Subsequent reduction of the volume to 3 mL in vacuo
and cooling of the solution for two days yielded a second crystal
fraction consisting of 1 and colourless crystals of 2.
CCDC-606897 to -606899 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
[1] Review articles: a) H. J. Breunig, Z. Anorg. Allg. Chem. 2005,
631, 621–631; b) L. Balazs, H. J. Breunig, Coord. Chem. Rev.
2004, 248, 603–621.
[2] a) G. Balazs, H. J. Breuning, E. Lork, Organometallics 2002,
21, 2584–2586; b) A. J. Ashe, Adv. Organomet. Chem. 1990, 30,
77–97; c) F. Calderazzo, R. Poli, J. Chem. Soc., Dalton Trans.
1984, 2365–2369; d) O. Mundt, G. Becker, M. Rössler, C. Wit-
thauer, Z. Anorg. Allg. Chem. 1983, 506, 42–58.
1: Yield: 0.12 g (41.7%). C64H76Bi2P2Si4 (1437.56): calcd. C 53.47,
1
H 5.33; found C 53.84, H 5.32. H NMR ([D8]THF): δ = 1.21 (s,
CCH3, 36 H), 7.28 (m), 7.50 (m), 7.54 (m): SiPh (40 H) ppm.
29Si{1H} NMR ([D8]THF): δ = 13.9 (m) ppm. 31P{1H} NMR
[3] N. Tokitoh, Y. Arai, R. Okazaki, S. Nagase, Science 1997, 277,
([D ]THF): δ = –202.0 (s) ppm. IR (KBr): ν =3132 (w), 3049 (m),
˜
8
78–80.
2961 (s), 2928 (s), 2889 (m), 2855 (s), 1958 (w), 1895 (w), 1822 (w),
1587 (w), 1567 (w), 1468 (m), 1426 (s), 1388 (w), 1360 (w) 1309
(w), 1262 (m), 1188 (w), 1155 (vw), 1099 (vs), 1006 (m), 935 (w),
884 (w) 814 (s), 737 (s), 701 (vs), 593 (s), 523 (vs), 485 (m), 408 (w)
cm–1. UV/Vis: λ (ε in Lmol–1 cm–1) = 820 (shoulder, 100), 564
(2944), 466 nm (shoulder, 1180).
[4] B. Tramley, C. D. Sofield, M. M. Olmstead, P. P. Power, J. Am.
Chem. Soc. 1999, 121, 3357–3367.
[5] H. J. Breunig, R. Rösler, E. Lork, Angew. Chem. 1998, 110,
3361–3363; Angew. Chem. Int. Ed. 1998, 37, 3175–3177.
[6] G. Linti, W. Köstler, Z. Anorg. Allg. Chem. 2002, 628, 63–66.
[7] L. Balazs, H. J. Breunig, E. Lork, Angew. Chem. 2002, 114,
2411–2414; Angew. Chem. Int. Ed. 2002, 41, 2309–2312.
[8] G. Balazs, L. Balazs, H. J. Breunig, E. Lork, Organometallics
2003, 22, 2919–2924.
2: Yield: about 0.02 g after sorting by hand. No satisfying elemen-
tal analysis can be obtained because of co-crystallisation of com-
1
pound 1. H NMR ([D8]toluene): δ = 1.20 (s, CCH3, 36 H), 7.06 [9] M. A. Beswick, N. Choi, A. D. Hopkins, Y. G. Lawson, M.
(m), 7.19 (m), 7.57 (m): SiPh (40 H) ppm. 29Si{1H} NMR ([D8]-
toluene): δ = 8.1 (pseudo-t, JPSi = 18.2 Hz) ppm. 31P{1H} NMR
([D8]toluene): δ = –199.8 (s) ppm. MS (EI = 70 eV, 180 °C): m/z
(%) = 1019 (22) [M+], 961 (3.4) [M+ – tBu], 904 (4.4) [M+ – 2 tBu],
779 (21) [M+ – SitBuPh2], 722 (36) [M+ – SitBuPh2 – tBu], 665 (37)
[M+ – SitBuPh2 – 2 tBu], 453 (100) [M+/2 – C4H8], 397 (100) [M+/
2 – 2 C4H8].
McPartlin, A. Rothenberger, D. Stalke, A. E. H. Wheatley,
D. S. Wright, Angew. Chem. 1999, 111, 3236–3238; Angew.
Chem. Int. Ed. 1999, 38, 3053–3055.
[10] S. Nagase, in The Chemistry of Organic Arsenic, Antimony and
Bismuth Compounds (Ed.: S. Patai), Wiley, New York, 1994.
[11] A. Dashti-Mommertz, B. Neumüller, Z. Anorg. Allg. Chem.
1999, 625, 954–960.
[12] M. Baudler, Y. Aktalay, K. Tebbe, T. Heinlein, Angew. Chem.
1981, 93, 1020–1022; Angew. Chem. Int. Ed. Engl. 1981, 11,
967–969.
[13] Overlap of the p-type lone pair at one phosphorus atom with
symmetry adapted anti bonding Si–P orbitals and/or empty d
orbitals at the other phosphorus atom.
[14] M. Ruck, D. Hoppe, B. Wahl, P. Simon, Y. Wang, G. Seifert,
Angew. Chem. 2005, 117, 7788–7792; Angew. Chem. Int. Ed.
2005, 44, 7616–7619.
3: Butyllithium solution (1.1 mL, 1.6 ) was added to a solution of
tBuPh2SiPH2 (0.24 g, 0.88 mmol) in Et2O 5 mL) at 0 °C. After stir-
ring for 10 min, this solution was added to a suspension of BiCl3
(0.19 g, 0.59 mmol) in Heptan (20 mL) at –70 °C. The reaction mix-
ture was warmed up to room temperature and then stirred for an
additional 16 h. Some of the solvent (20 mL) was removed in
vacuo. The resulting black-green solution was filtered to remove
the precipitated LiCl and elemental bismuth and cooled to –35 °C.
Red crystals of 3 were obtained over a period of some days. Yield:
0.1 g (22.6%). C64H76Bi2P4Si4 (1499.5): calcd. C 51.26, H 5.11;
[15] D. Nikolova, C. von Hänisch, Eur. J. Inorg. Chem. 2005, 378–
382.
[16] STOE-IPDS2 (Mo-Kα radiation, λ = 0.71073 Å). The struc-
tures were solved by direct methods and refined by full-matrix
least-squares techniques against F2 (Bi, P, Si, C refined aniso-
tropically, H atoms were calculated at ideal positions). Numeri-
cal absorption correction was applied for compound 1.
Received: May 22, 2006
1
found C 51.63, H 5.30. H NMR (C6D6): δ = 1.36 (s, SitBu, 9 H),
1.39 (s, SitBu, 9 H), 1.52 (s, SitBu, 18 H), 6.86 (m), 7.15 (m), 7.36
(m), 7.58 (m), 7.80 (m), 8.06 (m): SiPh (40 H) ppm. 31P{1H} NMR
([D8]toluol, 70 °C):
–113 (dd, JPP = 400 Hz, JPP = 87 Hz), –73.7 (t, JPP = 400 Hz)
δ
=
–256.6 (t, 2JPP
=
87 Hz),
1
2
1
Published Online: October 13, 2006
Eur. J. Inorg. Chem. 2006, 4770–4773
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4773