Phosphanimin- und Phosphaniminato-Komplexe des Zinks. Kristallstrukturen von [ZnCl2(Me3SiNP(CH2)4CMe3)]2, [ZnI2(Me3SiNPEt3)]2, [ZnI2{Me2Si(NPEt3)2}] und [ZnBr(NPMe3)]4· CH2Cl2/ Phosphaneimine and Phosphoraneiminato Complexes of Zinc. Crystal Structures of [ZnCl2(Me3SiNP(CH2)4CMe3)]2, [ZnI2(Me3SiNPEt3)]2, [Znl2{Me2Si(NPEt3)2}], and [ZnBr(NPMe3)]4· CH2Cl2

Abstract

Abstract The donor-acceptor complexes [ZnCl2(Me3SiNP(CH2)4CMe3)]2 (1)and [ZnI2(Me3SiNPEt3)]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(Me2Si(NPEt3)2)] (3). Znl2 and ZnBr2 react with the silylated phosphaneimines Me3SiNPR3(R = Me, Et) in the presence of NaF at elavated temperatures to give the phosphoraneiminato complexes [ZnI(NPEt3)]4 (4), [ZnBr(NPMe3)]4 (5) and [ZnBr(NPEt3)]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 Me3SiNP(CH2)4CMe3 do not lead to a phosphoraneiminato complex of zinc. 1: Space group P21/n, Z = 2; lattice dimensions at -60 °C: a = 903.3(2), b = 1217.9(3), c = 1591.6(2) pm, β = 93.94(1)°, R = 0.031. 2: Space group P21/n, Z = 2; lattice dimensions at -70°C: a = 947.9(2), b = 1219.2(2), c - 1527.1(2) pm, 0 = 91.17(1)°, β = 0.045. 1 and 2 form centrosymmetric dimeric molecules via Zn2X2 bridges (X = Cl, I); bond lengths Zn-N = 198.7(2) pm (1) and 199.0(6) pm (2). 3: Space group P412121 Z = 8; lattice dimensions at -90°C: a = b = 965.4(1), c = 2796.9(2) pm, R = 0.019.3 forms monomeric molecules with the Me2Si(NPEt3)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 P42/nmc, Z = 2; lattice dimensions at -70°C: a = b = 1146.9(6), c = 1437.9(7) pm, R = 0.060.