One-electron redox reactions involving chromium(0) and molybdenum(0) bis-1,3,5-trimethylbenzene derivatives

The reaction of M(η6-1,3,5-Me3C6H3)2, M = Cr, Mo, with the tetrahalides of Groups 4 and 5 elements proceeds with the monoelectronic oxidation of the metal bis-arene to the [M(η6-Me3C6H3)2]+ cation. In the case of MX4, M = Ti, X = Cl, Br, M = V, X = Cl, and of Nb2Cl10 the reduction products are the titanium(III), vanadium(III) halides and the niobium(IV) chloride, isolated as the solvate anions [MCl4(THF)2]− and [NbCl4(CH3CN)]−. The reaction of the tetrachloro complexes MCl4(THF)2, M = Zr, Hf, with Cr(η6-1,3,5-Me3C6H3)2 in THF produces the ionic [Cr(η6-1,3,5-Me3C6H3)2][MCl5(THF)], which has been characterized by single-crystal X-ray diffraction in the case of hafnium.