The reaction of [4,6-(MeO) 2 pmNHLi] (pm=2-pyrimidinyl) with 'ZnCl 2 ' gives the oxo-complex [Zn 4 {HN-4,6-(MeO) 2 pm} 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) 2 pm} 2 .TMEDA] (2) is obtained as its toluene solvate (2.toluene) by the reaction of ZnMe 2 with 4,6-(MeO) 2 pmNH 2 in the presence of TMEDA (Me 2 NCH 2 CH 2 NMe 2 ). Attempted in situ metallation of the primary phosphide [MeZnHP t Bu] n using Sb(NMe 2 ) 3 gives rise to the trimeric, Me 2 NH-solvated complex [MeZn(μ-HP t Bu).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.