Reactivity of a dithorium oxo complex from adventitious water

Abstract

The presence of adventitious water in the treatment of [ThCl₄(DME)₂] with two equivalents of [K(C₅Me₅)] results in the formation of the title bridging oxo complex, [{(C₅Me₅)₂ThCl}₂(μ-O)] (1). This complex can also be formed from the reaction of [(C₅Me₅)₂ThCl₂] with one equivalent of degassed water. The reactivity of the oxo complex was probed with Me₃SiCl and AlCl₃, resulting in the quantitative formation of [(C₅Me₅)₂ThCl₂]. Treatment of [{(C₅Me₅)₂ThCl}₂(μ-O)] with two equivalents of MeMgCl leads to [{(C₅Me₅)₂ThMe}₂(μ-O)] (2) which can be further treated with PhN(H)N(H)Ph, yielding [{(C₅Me₅)₂Th(PhNN(H)Ph)}₂(μ-O)] (3). Each complex has been characterized by spectroscopic and structural methods.