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

• Published in: Inorganica Chimica Acta Vol. 354; pp. 41 - 48
• Main Authors: Bashall, Alan, Cole, Jacqueline M, Garcı́a, Felipe, Primo, Ana, Rothenberger, Alexander, McPartlin, Mary, Wright, Dominic S
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 30.10.2003
• Subjects: Nitrogen; Phosphorus; X-ray crystallography; Zinc; X-ray crystallography; Phosphorus; Nitrogen; Zinc
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/S0020-1693(03)00375-X

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. The primary amido– and phosphido–Zn(II) complexes [Zn 4{HN-4,6-(MeO) 2pm} 6(μ 4-O)]·4thf ( 1·4thf), [Zn{HN-4,6-(MeO) 2pm} 2·TMEDA]·toluene ( 2·toluene) (TMEDA=Me 2NCH 2CH 2NMe 2) and [MeZn(μ-HP tBu)·NHMe 2] 3 ( 3) have been prepared and characterised structurally. Complexes 2 and 3 are the first bis(primary)amido and primary phosphido complexes of Zn.