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Co-ordination studies of tris(dimethylamino)phosphine oxide: Reactions with the covalent metal halides MCl3 (M = Ti, V and Cr), MCl4 (M = Ti, Zr, Hf and Sn) and SnI4

1980; Pergamon Press; Volume: 42; Issue: 8 Linguagem: Inglês

10.1016/0022-1902(80)80423-4

1878-1225

S. R. WADE, Gerald R. Willey,

Lanthanide and Transition Metal Complexes

Complexes of the type MCl3·3L where M = Ti, V and Cr; L = (Me2N)3P = O(HMPA) are described. Conductivity, IR and UV-visible spectral data correlates with a proposed fac-octahedral (C3v) configuration. For the Cr(III) species, geometrical isomerisation has been observed leading to isolation of the mer-isomer (C2v). Spectral (1H, 31P and 13C NMR and far IR) measurements for the six co-ordinate series MCl4·2HMPA (M = Ti, Zr, Hf and Sn) and SnI4·2HMPA correlate fully with a trans(D4h) arrangement of the ligands. Complexes 2TiCl4·HMPA and SnCl4·HMPA have been isolated and characterised. Spectral properties of these diamagnetic compounds are related to the confacial bioctahedral and dimeric halogen-bridged (C2h) structures respectively.