Reaktion von DioxomoIybdän(VI)-Komplexen mit O-Methyl-thiocarbazat Darstellung und Charakterisierung von Schiffbase-, Hydrazido- und Diazenido-Komplexen des Molybdäns / Reaction of Dioxomolybdenum(VI) Complexes with O-Methylthiocarbazate Synthesis and Characterization of Schiffbase, Hydrazido and Diazenido Complexes of Molybdenum

Abstract

<jats:title>trans</jats:title><jats:p>The reaction of NH<jats:sub>2</jats:sub>NHC(S)OR, (R = Me, Et) with MoO<jats:sub>2</jats:sub>(acac)<jats:sub>2</jats:sub> yields the dimeric complexes MO<jats:sub>2</jats:sub>O<jats:sub>3</jats:sub>(MeC(O)CHC(Me)NNC(S)0R)<jats:sub>2</jats:sub> (1) with the planar O = Mo - O - Mo = O group. The tetradentate O,N,S-donor ligand is formed through condensation of acetylacetone with the organohydrazine. The reactions of NH<jats:sub>2</jats:sub>NHC(S)OMe with MoO<jats:sub>2</jats:sub>(S<jats:sub>2</jats:sub>CNEt<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub> and MoO<jats:sub>2</jats:sub>(ONEt<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub> give the diazenido hydrazido complexes Mo(NNC(S)OMe)(NH<jats:sub>2</jats:sub>NC(S)OMe)(S<jats:sub>2</jats:sub>CNEt<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>·CH<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub><jats:bold>(2) </jats:bold>and Mo(NNC(S)OMe)(NH<jats:sub>2</jats:sub>NC(S)OMe)<jats:sub>2</jats:sub>(ONEt<jats:sub>2</jats:sub>) <jats:bold>(4). </jats:bold>The metal atoms in both compounds are seven coordinated and contain the approximately linear diazenido ligand NNC(S)OMe and one <jats:bold>(2) </jats:bold>or two <jats:bold>(4) </jats:bold>N,S-chelating hydrazido(1-) ligands NH<jats:sub>2</jats:sub>NC(S)OMe. <jats:bold>2 </jats:bold>has crystallographically imposed mirror symmetry. Recrystallization of <jats:bold>2 </jats:bold>from toluene in air gives the asymmetric dinuclear complex (Et<jats:sub>2</jats:sub>NCS<jats:sub>2</jats:sub>)(O)Mo(μ-NNC(S)OMe)<jats:sub>2</jats:sub>Mo(S<jats:sub>2</jats:sub>CNMe<jats:sub>2</jats:sub>) <jats:bold>(3). </jats:bold>The Mo-Mo distance is 267.0(2) pm. One Mo site has square pyramidal MoOS<jats:sub>2</jats:sub>N<jats:sub>2</jats:sub> geometry, the other trigonal prismatic MoN<jats:sub>2</jats:sub>S<jats:sub>4</jats:sub> geometry. The coordination of the bridging N atoms is slightly pyramidal. The compounds <jats:bold>1, 2 </jats:bold>and <jats:bold>3 </jats:bold>have been further characterized by vibrational spectroscopy.</jats:p>