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Formations and electrochemical behavior of mononuclear and binuclear molybdenum dithiolene complexes with nitrosyl ligands: Evidence for the formation of a coordinatively unsaturated species [CpMo(NO)(dithiolene)]
Authors:Mitsushiro Nomura  Souichi Sakaki  Yoshimasa Hoshino
Institution:a Department of Chemistry, Faculty of Science and Technology, Sophia University, Kioi-cho 7-1, Chiyoda-ku, Tokyo 102-8554, Japan
b Department of Natural Science, Faculty of Education, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract:The one-pot reaction of CpMo(NO)(CO)2] with elemental sulfur and dimethyl acetylenedicarboxylate (C2Z2 (Z = COOMe)) gave the 2+2] cycloadduct of the mononuclear molybdenum dithiolene complex CpMo(NO)(S2C2Z2)(C2Z2)] (1), and some binuclear complexes:CpMo(NO)(S2C2Z2)]2 (2), Cp2Mo2(NO)2S2(S2C2Z2)] (3) and CpMo(NO)S2]2 (4).The reaction of CpMo(NO)(Cl)(μ-Cl)]2 with Odouble bond; length as m-dashC{S2C2(COOMe)2} in the presence of sodium methoxide also produced complex 2 and the paramagnetic CpMo bisdithiolene complex CpMo(S2C2Z2)2] (5, Z = COOMe).The structures of complexes 1-5 were determined by X-ray crystal structure analysis.The nitrosyl ligands of complexes 1-4 showed a linear coordination to the molybdenum center (the Mo-N-O bond angles = 169-174°), and their N-O bond lengths were 1.17-1.20 Å.In the binuclear complexes 2-4, two nitrosyl ligands were placed at cis-position.Complexes 1 and 2 were characterized by cyclic voltammetry and spectroelectrochemistry (visible and IR). The electrochemical reduction of the dimeric complex 2 formed the monomeric dithiolene complexCpMo(NO)(S2C2Z2)] (X) whose lifetime was several minutes. When the anion X was electrochemically oxidized, the coordinatively unsaturated species X was generated, but it was immediately dimerized to afford the original dimeric complex 2. The reduction of the complex 1 included the elimination of the bridged DMAD moiety (C2Z2) to give the anion X.
Keywords:Molybdenum  Dithiolene  Mononuclear  Nitrosyl  X-ray structure  Electrochemistry
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