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

The reaction of [4,6-(MeO)2pmNHLi] (pm=2-pyrimidinyl) with ‘ZnCl2’ gives the oxo-complex [Zn4{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 ZnMe2 with 4,6-(MeO)2pmNH2 in the presence of TMEDA (Me2NCH2CH2NMe2). Attempted in situ metallation of the primary phosphide [MeZnHP^tBu]n using Sb(NMe2)3 gives rise to the trimeric, Me2NH-solvated complex [MeZn((mu)-HP^tBu)·NHMe2]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.