Five-co-ordinate complexes

Abstract
The complexes VX3,2L (X = Cl and Br; L = NMe3, SMe2, and C4H8S), VCl3,2SEt2, and CrCl3,2NMe3 have been prepared and shown to be monomeric in solutions in non-donor solvents. Structural measurements (dipole moments, i.r., visible, and u.v. spectra) indicate that the metal atoms have trans-trigonal-bipyramidal configurations. In the solid state the trimethylamine complexes also contain five-co-ordinate metal atoms, but spectral evidence shows that the sulphur complexes contain six-co-ordinate vanadium, presumably through dimerisation. Reactions of vanadium(III) chloride with higher alkyl sulphides did not give five-co-ordinate complexes; vanadium(IV) chloride was reduced by dialkyl sulphides and thiols.

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