H. Weichmann, J. Meunier-Piret
Oct 1, 1993
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0
Influential Citations
8
Citations
Journal
Organometallics
Abstract
A series of 1-phenyl-1-chalcogeno-4-methyl-4-chloro-1lambda5,4-phosphastanninanes Me(Cl)Sn(CH2-CH2)2P(E)Ph with E = S, Se, O (7-9) has been synthesized by chlorodemetalation of the related tetraorganotin derivatives Me2Sn(CH2-CH2)2P(E)Ph (1-3) with Me2SnCl2. Sn-119, P-31, and H-1 NMR studies in nonpolar solvents show that 7-9 exhibit a P=E...Sn coordination which is intramolecular for 7 and 8 (E = S, Se) and intermolecular for 9 (E = O). In donor solvents the intramolecular interaction of 7 and 8 is no longer present. The molecular structures of 7-9 were determined by X-ray analysis. The structure determination of 7 gave the monoclinic space group P2(1)/c (a = 12.256(15), b = 9.293(6), c = 12.622(13) angstrom; beta = 96.64(10)degrees; V = 1427.9(25) angstrom3; Z = 4; R = 0.040). 8 crystallizes in the orthorhombic space group Pccn (a = 22.703(3), b = 16.910(22), c = 7.523(4) angstrom; V = 2888.1(51) angstrom3; Z = 8; R = 0.053). 9 has the triclinic space group P1 (a = 7.606(3), b = 10.179(2), c = 9.883(2) angstrom; alpha = 117.97(2), beta = 96.58(3), gamma = 87.80(3)degrees; V = 671.2(3) angstrom3; Z = 2; R = 0.0395). In the solid state 7-9 also exhibit pentacoordination at the tin with the ligand polyhedron approaching an ideal trigonal bipyramid in the order 7 < 8 < 9. 9 exists as dimers with intermolecular P=O...Sn contacts and a chair conformation for the 1lambda5,4-phosphastanninane ring system, whereas 7 and 8 are monomeric with intramolecular P=E...Sn coordination and a boat conformation of the six-membered ring.