Synthesis and structural characterization of arsinoamides - early transition metal (Zr and Hf) and main group metal (Al, In, Sn, and Pb) complexes.

Abstract

By reaction of MCl4 (M = Zr, Hf) with 2 equiv. of [(Mes2AsNPh){Li(OEt2)2}], the first group 4 metal arsinoamide complexes [(Mes2AsNPh)2MCl2(THF)] were synthesized. They feature two weak M-As interactions. After formally replacing the chloride atoms by the amido ligands [NMe2]-, a more diverse M-As interaction arises in [(Mes2AsNPh)2M(NMe2)2]: only one M-As contact can be observed with a substantially shorter distance. This type of interaction may originate from the steric effect of the substituents on the metal center. In addition, the coordination behavior of arsinoamide in main group metal chemistry was investigated. Thus, arsinoamide complexes of Al(iii), In(iii), Sn(ii) and Pb(ii) are reported. In contrast to the group 4 complexes, no M-As interaction can be detected in these four complexes.