Zwitterionic and bis-amido zinc complexes with bulky bis(phosphanylamino)benzene ligands:: Synthesis, reactivity, and molecular structures of [ZnCl2(1,2-{N(PHMes2)}2C6H4-K2N,N′)], [ZnPr{1-N(PMes2)-2-N(PHMes2)C6H4-K2N,N′}], and [Zn{1-N(PMes2)-2-N(μ-PMes2)C6H4-K3N,N′,P}]2

The reaction of [ZnCl2(THF)(2)] with 1,2-{NH(PMeS2)}(2)C6H4 (Mes = 2,4,6-Me3C6H2) yielded the unusual Zn-II complex [ZnCl2(1,2-{N(PHMes(2))}(2)C6H4-kappa(2)N,N')] (1), in which a proton transfer from nitrogen to phosphorus had occurred. ZnR2 reacted with 1,2-{NH(PMes(2))}(2)C6H4 to give the zwitterionic compounds [ZnR{1-N(PMes(2))-2-N(PHMes(2))C6H4-kappa(2)N,N'}] (R = Pr (2a), Et (2b)). The bis-amido complex [Zn{1-N(PMes(2))-2-N(mu-PMes(2))C6H4-kappa(3)N,N',P}](2) (3) was obtained from ZnCl2 and 1,2-{LiN(PMes(2))}(2)C6H4. The Zn-II alkoxide complex [Zn{1-N{PMes(2)CH(2)CH(Me)O}-2-N(PMes(2))C6H4-kappa(3)N,N',O}](2) (4) was obtained from the reaction of 2a with propylene oxide. Complexes 1-4 were characterized spectroscopically (H-1, C-13, P-31 NMR; MS; IR) and by X-ray structure determination.