Nitrido-azido-Komplexe des Molybdäns(VI) Synthese und Kristallstruktur von MoN(N3)3(NC5H5) / Nitrido Azido Complexes of Molybdenum (VI) Synthesis and Crystal Structure of MoN(N3)3(NC5H5)

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Abstract The explosive nitrido azido complexes MoN(N3)Cl2 · py and MoN(N3)3py are prepared by the reaction of MoCl4(py)2 with (CH3)3SiN3 in 1,2-dichloroethane. Both compounds hydrolyze quickly in moist air. After separation of the insoluble, black MoN(N3)Cl2 · py from the solution of MoN(N3)3py, the latter can be obtained in form of monoclinic, red crystals of the space group C2/c. Its structure consists of monomeric complexes, wherein the Mo atom has a square pyramidal coordination. The nitrido ligand occupies the apex and forms a strong multiple bond of 163.4 pm to the Mo atom. σ-Bonds of different strength exist between the Mo atom and the basal ligands: MO-N3 - 204.3 pm; Mo-py = 225.8 pm. The α-N atoms of the azido groups are sp2 hybridized, with their lone pair pointing away from the nitrido ligand. The pyridine ligand forms an angle of 61.6° to the basal plane of the coordination polyhedron.