Reduced Arene Complexes of Hafnium Supported by a Triamidoamine Ligand

A series of hafnium complexes with a reduced arene of the general formula [K(L)][Hf(Xy‐N(3)N)(arene)] (Xy‐N(3)N={(3,5‐Me(2)C(6)H(3))NCH(2)CH(2)}(3)N(3−), L=THF, 18‐crown‐6; arene=C(10)H(8) (2−), C(14)H(10) (2−)) mimic the chemistry of hafnium in its formal oxidation state +II. All compounds were obtained upon reduction of the chlorido complex [HfCl(Xy‐N(3)N)(thf)] with two equivalents of potassium naphthalenide or anthracenide. The reducing nature and the basicity of the reduced anthracene ligand were explored in the reaction of benzonitrile and azobenzene, and by deprotonation of tert‐butylacetylene, respectively. The reduction of benzonitrile provides an initial double nitrile insertion product under kinetic control that rearranges after extrusion of one of the inserted nitriles to a hafnium imido complex as the thermodynamic product. The reduction of azobenzene resulted in a diphenylhydrazido(2−) complex. Treatment of terminal alkynes with the anthracene or diphenylhydrazido(2−) complex led to the selective protonation of the corresponding dianionic ligand.