SYNTHESES AND CRYSTAL-STRUCTURES OF THE P HOSPHANEIMINE COMPLEXES MCL2(ME3SINPME3)2 WITH M = ZN AND CO, AND COCL2(HNPME3)2

The molecular complexes MCl2(Me3SiNPMe3)2 M = Zn, Co) have been prepar ed by the reaction of the dichlorides of zinc and cobalt with Me3SiNPM e, in CH3CN and CH2Cl2, respectively, whereas the complex CoCl2(HNPMe3 )2 has been prepared by the reaction of CoCl2 with NaF in boiling acet onitrile in the presence of Me3SiNPMe3. All complexes were characteriz ed by IR spectroscopy and by crystal structure determinations. The com plexes MCl2(Me3SiNPMe3)2 crystallize isotypically. ZnCl2(Me3SiNPMe3)2: Space group P2(1)2(1)2(1), Z = 4, 2677 observed unique reflections, R = 0.024. Lattice dimensions at -70-degrees-C: a = 1 243.6; b = 1 319. 0; c = 1 464.7 pm. CoCl2(Me3SiNPMe3)2: Space group P2(1)2(1)2(1), Z = 4,3963 observed unique reflections, R = 0,071. Lattice dimensions at - 80-degrees-C: a = 1236.3; b = 1317.4; c = 1457.6 pm. CoC12(HNPMe3)2 . CH2Cl2: Space group Pbca, Z = 8, 1354 observed unique reflections, R = 0.055. Lattice dimensions at -80-degrees-C: a = 1247.3; b = 998.4; c = 2882.4 pm. All complexes have monomeric molecular structures, in whi ch the metal atoms are coordinated in a distorted tetrahedral fashion by the two chlorine atoms and by the nitrogen atoms of the phosphaneim ine molecules.