TELLURIUM POLYCATIONS BY OXIDATION OF TELLURIUM WITH TUNGSTEN HALIDES - SYNTHESES AND CRYSTAL-STRUCTURES OF TE(6)(WOCL(4))(2) AND TE(6)I(2)(WCL(6))(2)

WOCl4 reacts at 200-degrees-C with tellurium in a sealed, evacuated ampoule with the formation of Te6(WOCl4)2. The structure consists of six-membered tellurium rings in a boat conformation with significant transannular interactions and of pyramidal WOCl4 units which are linked by linear asymmetric O...W = O bridges to polymeric (WOCl4)n chains. The observed paramagnetism is consistent with the ionic formulation Te6(2+)[(WOCl4-)2]n. In the reaction of WCl6, I2 and Te in a 2:1:6 ratio Te6I2(WCl6)2 is formed at 150-degrees-C. The crystal structure consists of Te6I2(2+) cations and of slightly distorted octahedral WCl6- anions. The Te6I2(2+) ions are isostructural with Se6I2(2+) and consist of a six-membered ring of Te atoms in the chair conformation with two I atoms bound in the 1,4-positions.