Direct electrochemical synthesis of neutral and anionic chloro- and bromo-complexes of titanium, zirconium, and hafnium

Abstract
Electrochemical oxidation of titanium, zirconium, or hafnium(IV) in the presence of a solution of chlorine or bromine (X) in acetonitrile (L) leads to direct synthesis of MX4L2 species in good yield. These compounds are easily transformed into other neutral adducts. On addition of tetraalkylammonium salts to the solution phase, the products are the salts (R4N)MCl5 or (R4N)2MBr6, except that with titanium Et4NTiBr4 was also formed under some conditions. The advantages of this method are discussed, and a possible reaction mechanism proposed.

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