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Synthesis, structure, and redox behaviour of a novel cis-dioxomolybdenum(VI) dinuclear complex with a quadradentate dithiocarbamate |
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| Authors: | Kei Unoura Yuko AbikoAkira Yamazaki Yoshikiyo KatoDarren C Coomber Gary D FallonKoichi Nakahara Alan M Bond |
| Institution: | a Department of Material and Biological Chemistry, Yamagata University, 1-4-12 Kojirakawa-machi, Yamagata 990-8560, Japan b School of Chemistry, Monash University, Clayton, Victoria 3800, Australia c Suntory Ltd. Research Centre, 1-1-1 Wakayamadai, Shimamoto-cho, Mishima-gun, Osaka 618-8503, Japan |
| Abstract: | A novel dinuclear cis-dioxomolybdenum(VI) complex {MoO2(Bz2endtc)}2] coordinated with a quadradentate dithiocarbamate (Bz2endtc2−: ((2-(dithiocarboxybenzylamino)ethyl)benzylamino)-methanedithioate(2−)) has been synthesised. The structural features of {MoO2(Bz2endtc)}2] have been elucidated by X-ray crystal analysis, elemental analysis and 13C NMR, IR and FAB+ mass spectroscopy: two almost identical cis-dioxomolybdenum(VI) centres are bridged by the two Bz2endtc2− ligands and each molybdenum(VI) centre has a distorted octahedral geometry with four sulphur atoms and two terminal oxo ligands lying in a cis position to each other. There is unlikely to be electronic interaction between the two cis-dioxomolybdenum(VI) centres in {MoO2(Bz2endtc)}2] because the MoMo distance is long (=7.337 Å). In the {MoO2(Bz2endtc)}2]/PPh3 system, the oxygen atom transfer reaction (Eq. (A)) occurs to give a tetranuclear oxomolybdenum(VI,V) complex formulated as MoO2(Bz2endtc)2Mo2O3(Bz2endtc)2MoO2] which has one μ-oxomolybdenum(V) moiety. (A) |
| Keywords: | Molybdenum complexes Dithiocarbamates Oxo transfer Kinetics and mechanism Electrochemistry |
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