Phosphaneimine and phosphoraneiminato complexes of zinc. Crystal structures of [ZnCl2(Me(3)SiNP(CH2)(4)CMe(3))](2), [ZnI2(Me(3)SiNPEt(3))](2), [ZnI2{Me(2)Si(NPEt(3))(2)}], and [ZnBr(NPMe(3))](4)center dot CH2Cl2

The donor-acceptor complexes [ZnCl2(Me(3)SiNP(CH2)(4)CMe(3))](2) (1) and [ZnI2(Me(3)SiNPEt(3))](2) (2) have been prepared from the zinc dihalides and the corresponding silylated phosphaneimines in CH2Cl2. Thermolysis of 2 leads to the formation of [ZnI2(Me(2)Si(NPEt(3))(2))] (3). ZnI2 and ZnBr2 react with the silylated phosphaneimines Me(3)SiNPR(3) (R = Me, Et) in the presence of NaF at elevated temperatures to give the phosphoraneiminato complexes [ZnI(NPEt(3))](4) (4), [ZnBr(NPMe(3))](4) (5) and [ZnBr(NPEt(3))](4) (6), respectively, which according to the IR spectra and to a crystal structure determination of 5 form heterocubane structures. The corresponding reactions with the more bulky phosphaneimine Me(3)SiNP(CH2)(4)CMe(3) do not lead to a phosphoraneiminato complex of zinc. 1: Space group P2(1)/n, Z = 2; lattice dimensions at -60 degrees C: a = 903.3(2), b = 1217.9(3), c = 1591.6(2) pm, beta = 93.94(1)degrees, R = 0.031. 2: Space group P2(1)/n, Z = 2; lattice dimensions at -70 degrees C: a = 947.9(2), b = 1219.2(2), c = 1527.1(2) pm, beta = 91.17(1)degrees, R = 0.045. 1 and 2 form centrosymmetric dimeric molecules via Zn(2)X(2) bridges (X = Cl, I); bond lengths Zn-N = 198.7(2) pm (1) and 199.0(6) pm (2). 3: Space group P4(1)2(1)2, Z= 8; lattice dimensions at -90 degrees C: a = b = 965.4(1), c = 2796.9(2) pm, R = 0.019. 3 forms monomeric molecules with the Me(2)Si(NPEt(3))(2) ligand as chelating agent to give a planar ZnN2Si four-membered ring with Zn-N distances of 207.0(2) pm. 5: Space group P4(2)/nmc, Z = 2; lattice dimensions at -70 degrees C: a = b = 1 146.9(6), c = 1437.9(7) pm, R = 0.060.