Sur la réaction du chlorure de nitrosyle avec le tétrachlorure de vanadium (IV)

Summary

The reaction of excess nitrosyl chloride with vanadium tetrachloride under specific conditions furnishes the previously unreported compound VCl₄, 2NOCl. The formation of a 1∶2 adduct shows that vanadium (IV) can behave as a typical tetravalent metal in the M^IVCl₄-NOCl system. Spectroscopic measurements reveal both nitrosonium and hexachlorometallate ions in the addition compound and indicate structural analogy with (NO)₂-TiCl₆. The complex may thus be designated as dinitrosonium hexachlorovanadate, (NO)₂VCl₆. However, this compound is probably not purely ionic, since the relatively low frequency observed for the IR-absorption of the NO+ ion (2146 cm⁻¹ compared with the normal range ∼2150 to 2400 cm⁻¹) and the appreciable volatility of the compound suggest a significant degree of covalent bonding.