Die Kristallstrukturen von [MoCl2(NO)2(OPEt3)]2, [MoCl3(NO)(OPPh3)2•MoCl4(OPPh3)2], [MoCl2(NO)(PPh3)2(CH3CN)] und [MoCl4(NPPh3)(OPPh3)] / The Crystal Structures of [MoCl2(NO)2(OPEt3)]2, [MoCl3(NO)(OPPh3)2 • MoCl4(OPPh3)2], [MoCl2(NO)(PPh3)2(CH3CN)], and [MoCl4(NPPh3)(OPPh3)]

Abstract

The title compounds have been prepared by reactions of MoCl2(NO)2 with PPh3, OPPh3, or Me3SiNPR3 (R = Et, Ph) in dichloromethane and acetonitrile suspension, respectively. All complexes were characterized by IR spectroscopy and by crystal structure determinations. [MoCl2(NO)2(OPEt3)]2: Space group C2/c, Z = 4, 2950 observed unique reflections, R = 0.029. Lattice dimensions at —70 °C: a = 2390.5(11), b = 875.5(5), c = 1399.1(6) pm, β = 113.18(2)°. The complex forms a centrosymmetric dimer with MoCl2Mo bridges, the nitrosyl groups being in a cis-arrangement. The OPEt3 ligand is coordinated in trans position to one of the nitrosyl ligands. [MoCl3(NO)(OPPh3)2 • MoCl4(OPPh3)2]: Space group P21/c, Z = 4, 10243 observed unique reflections, R = 0.060. Lattice dimensions at —60 °C: a = 1900.4(3), b = 1689.1(5), c = 2209.3(7) pm, β = 95.92(2)°. The structure consists of the two independent complexes [MoCl3(NO)(OPPh3)2] and [MoCl4(OPPh3)2]. In both complexes the OPPh3 groups are in a cis-arrangement at the octahedrally coordinated Mo atoms; in the nitrosyl complex one of the OPPh3 molecules is in trans-position to the nitrosyl ligand. [MoCl2(NO)(PPh3)2(CH3CN)]: Space group P21/n, Z = 4, 5107 observed unique reflections, R = 0.028. Lattice dimensions at 20 °C: a = 1006.5(2), b = 1527.2(2), c = 2342.3(2) pm, β = 90.97(1)°. The PPh3 molecules are in trans-positions to one another at the octahedrally coordinated Mo atom, whereas the acetonitrile molecule is in trans-position to the nitrosyl ligand. [MoCl4(NPPh3)(OPPhi)]: Space group P21, Z = 2, 3323 observed unique reflections, R = 0.057. Lattice dimensions at —70 °C: a = 985.7(8), b = 1471.2(9), c = 1215.9(11) pm, β = 100.50(3)°. The OPPh3 molecule coordinates in trans-position to the phosphorane iminato ligand at the octahedrally coordinated Mo atom.