Phosphanimin-Komplexe von Mangan(II)halogeniden. Die Kristallstrukturen von [MnCl2(Me3SiNPEt3)]2, [Mnl2(Me3SiNPEt3)2] und [MnI2(Me2Si(NPEt3)2)] / Phosphaneimine Complexes of Manganese(II)halides. The Crystal Structures of [MnCl2(Me3SiNPEt3)]2, [Mnl2(Me3SiNPEt3)2] and [MnI2(Me2Si(NPEt3)2)

Abstract

The phosphaneimine complexes [MnCl2(Me3SiNPEt3)]2 (1) and [MnI2(Me3SiNPEt3)2] (2) have been prepared by the reaction of Me3SiNPEt3 with MnCl2 and Mnl2, respectively. Thermal decomposition of 2 leads to the chelate complex [MnI2(Me2Si(NPEt3)2)] (3) by cleaving SiMe4. The complexes are characterized by IR spectroscopy and by crystal structure determinations. 1: Space group P21/c, Z = 4, structure solution with 5062 observed unique reflections, R = 0.047. Lattice dimensions at -55 °C: a = 1175.8(5), b = 1634.5(2), c = 1740.2(8), β = 99.58(2)°. 1 forms dimeric molecules via chloro bridges and a cis-arrangement of the Me3SiNPEt3 donor molecules with Mn-N bond lengths of 210.4(5) and 208.2(4) pm. 2: Space group P 41212, Z = 4, structure refinement with 1633 independent reflections, 1072 observed unique reflections, R = 0.053. Lattice dimensions at -60 °C: a = b = 949.5(1), c = 3345.2(7) pm. 2 forms monomeric molecules with tetrahedrally coordinated Mn atoms and Mn-N bond lengths of 220.7(13) pm. 3: Space group P21/c, Z = 4, structure refinement with 8419 independent reflections, 4584 observed unique reflections, R = 0.047. Lattice dimensions at 20 °C: a = 1343.3(1), b = 2508.2(2), c = 1535.1(1) pm, β = 91.742(5)°. 3 forms monomeric molecules with the [Me2Si(NPEt3)2] ligand bound in a chelating fashion with Mn-N bond lengths of 212.9 pm in average.