Reaktion von Oxomolybdän-Komplexen mit Alkyldithiocarbazaten. Darstellung und Charakterisierung von Hydrazido- und Diazenido-Komplexen des Molybdäns / Reaction of Oxomolybdenum Complexes with Alkyldithiocarbazates. Synthesis and Characterization of Hydrazido- and Diazenido Complexes of Molybdenum
(2).The reaction of alkyldithiocarbazates NH2NHC(S)SR′ with MoO2(S2CNR2)2 R, R′ = Me, Et) yields the diazenido hydrazido complexes Mo(NNC(S)SR′)(NH2NC(S)SR′)(S2CNR2)2 (1), reaction with the molybdenum hydroxylamidate complex MoO2(ONMe2)2 gives the diazenidobis( hydrazido) complex Mo(NNC(S)SMe)(NH2NC(S)SMe)2(Me2NO)-CH3OH The crystal structures of 1 a (R = Me, R′ = Et) and 2 have been determined. The metal atoms in 1 a and 2 are seven coordinated and have MoN2S5 and MoN3O2S2 ligand arrays, respectively. Both compounds contain the approximately linear diazenido ligand NNC(S)SR in addition to one (1a) or two (2) N,S-chelating hydrazido(1-) ligands NH2NC(S)SR. When 1a is treated with HCl, the dimeric complex (Me2NCS2)(O)Mo(μ-NNC(S)SEt)2 Mo(S2CNMe2) (4) is obtained. X-ray crystallography showed 4 to be an asymmetric dinuclear complex, with a Mo-Mo distance of 267.2(1) pm. One Mo site has a square pyramidal MoOS2N2 geometry, while the other one has an approximately trigonal prismatic MoN2S4 geometry. The mean N-N distance in 4 is 135(1) pm. The reaction of NH2NHC(S)SMe with MoO2(acac)2 yields Mo(Me2CNNC(S)SMe)(NNC(S)SMe)(MeSC(S)NNC(S)SMe) (3). Its structure has been determined by X-ray crystallography. 3 contains a unique combination of three different N- and S-chelating ligands: the Schiff base Me2C=NNC(S)SMe, the highly bent bidentate diazenido ligand NNC(S)SMe (∡ Mo-N-N = 142.1(5)°), and the novel planar tridentate ligand MeSC(S)NNC(S)SMe. The latter can be taken as neutral diacyldiazene or, more likely, as the dianion of the as yet unknown MeSC(S)NH -NHC(S)SMe. The N - N distance in this ligand is 136.1(9) pm.