Structures and bonding in some chloro complexes of trivalent metals

Abstract

Compounds of the type (cation+)MCl4- form isomorphous series when (cation+) = Ph4P+ and Ph4As+, and M = Al, Ga, In, Tl, V, and Fe in their trivalent states. X-ray data, infrared data, and for the vanadium compounds, magnetic and electronic spectral data, also suggest that the series is isomorphous, with the MCl4- ion having a slightly distorted tetrahedral symmetry. 35Cl nuclear quadrupole resonance results for the Al and Tl compounds indicate a site symmetry of S4 for the MCl4- ion. Magnetic data for the vanadium compounds, and also for (Bun)4NVCl4, show some antiferromagnetic interaction of the VCl4- ions in these lattices. Infrared data are also presented for (Ph4As)2InCl5, Ph4PSbCl4, Ph4AsSbCl4, Ph4PBiCl4, and PhdAsTiCl4, none of which appears to contain tetrahedral MCl4- ions.