Primary amido and phosphido complexes of zinc: potential precursors to heterometallic arrangements

Abstract

The reaction of [4,6-(MeO) 2pmNHLi] (pm=2-pyrimidinyl) with ‘ZnCl 2’ gives the oxo-complex [Zn 4{HN-4,6-(MeO) 2pm} 6( 4-O)]·4thf ( 1·4thf), containing a tetrahedral arrangement of four Zn centres which surround a central O 2− ion, as a result of the presence of lattice hydrolysis of the Zn salt. The bis(primary)amido complex [Zn{HN-4,6-(MeO) 2pm} 2·TMEDA] ( 2) is obtained as its toluene solvate ( 2·toluene) by the reaction of ZnMe 2 with 4,6-(MeO) 2pmNH 2 in the presence of TMEDA (Me 2NCH 2CH 2NMe 2). Attempted in situ metallation of the primary phosphide [MeZnHP tBu] n using Sb(NMe 2) 3 gives rise to the trimeric, Me 2NH-solvated complex [MeZn(μ-HP tBu)·NHMe 2] 3 ( 3). The solid-state structures of 1, 2 and 3 are reported. Complexes 2 and 3 are the first bis(primary)amido and primary phosphido complexes of Zn.