caa a22 4500 477085377 CHVBK 20180405111502.0 cr unu---uuuuu 170330e19960901xx s 000 0 eng 10.1007/BF01171191 doi (NATIONALLICENCE)springer-10.1007/BF01171191 Syntheses and structures of Tetranuclear Cluster complexes of molybdenum [Mo4(μ3-S)2(μ2-S)4 X 2-(PMe3)6] ( X [Elektronische Daten] SH, Cl, Br, I, SCN) and [Mo4(μ3-S)2-(μ2-S)4 (dtc)2(PMe3)4] (dtc = diethyldithiocarbamate) [Kiyoshi Tsuge, Setsuko Mita, Hiroko Fujita, Hideo Imoto, Taro Saito] A molybdenum cluster complex [Mo4(μ3-S)2(μ2-S)4)(SH)2(PMe3 6] has been synthesized by the reaction of (NH4)2Mo3S13 with trimethylphosphine. The cluster core is composed of four molybdenum atoms arranged in the rhombus bridged by two capping and four bridging sulfur atoms. Two SH and six tri-methylphosphine ligands are coordinated to the terminal positions. The mean oxidation stares of molybdenum is +3.5 and there are five Mo-Mo bonds consistent with ten metal cluster electrons. The complex has been converted into [Mo4(μ3-S)2(μ2-S)4 X 2(PMe3)6] (X=Cl, Br, I, SCN) and [Mo4μ3-S2(μ2-S)4 (die)2(PMe3)4] (dtc - diethyldithiocarbamate). In the case of the dtc complex, two terminal trimetlaylphosphine ligands are displaced and dtc ligands are coordinated in chelate fashion. The structures of the SH, Cl, Br, and dtc complexes have been determined by X-ray crystallography. Molecular orbital calculations with DV-Xα method has shown large HOMO-LUMO gaps (1.52-1.74eV) for [Mo4S6 X 2(PH3)4] (X= SH, Cl, and Br). Plenum Publishing Corporation, 1996 Molybdenum nationallicence tetranuclear cluster nationallicence trimethylphosphine nationallicence sulfide nationallicence diethyldithiocarbamate nationallicence Tsuge Kiyoshi Institute for Molecular Science, 444, Okazaki, Japan aut Mita Setsuko Department of Chemistry, School of Science, The University of Tokyo, Bunkyo-ku, 113, Tokyo, Japan aut Fujita Hiroko Department of Chemistry, School of Science, The University of Tokyo, Bunkyo-ku, 113, Tokyo, Japan aut Imoto Hideo Department of Chemistry, School of Science, The University of Tokyo, Bunkyo-ku, 113, Tokyo, Japan aut Saito Taro Department of Chemistry, School of Science, The University of Tokyo, Bunkyo-ku, 113, Tokyo, Japan aut Journal of Cluster Science Kluwer Academic Publishers-Plenum Publishers 7/3(1996-09-01), 407-421 1040-7278 7:3<407 1996 7 10876 https://doi.org/10.1007/BF01171191 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/BF01171191 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Tsuge Kiyoshi Institute for Molecular Science, 444, Okazaki, Japan aut NATIONALLICENCE 700 1- Mita Setsuko Department of Chemistry, School of Science, The University of Tokyo, Bunkyo-ku, 113, Tokyo, Japan aut NATIONALLICENCE 700 1- Fujita Hiroko Department of Chemistry, School of Science, The University of Tokyo, Bunkyo-ku, 113, Tokyo, Japan aut NATIONALLICENCE 700 1- Imoto Hideo Department of Chemistry, School of Science, The University of Tokyo, Bunkyo-ku, 113, Tokyo, Japan aut NATIONALLICENCE 700 1- Saito Taro Department of Chemistry, School of Science, The University of Tokyo, Bunkyo-ku, 113, Tokyo, Japan aut NATIONALLICENCE 773 0- Journal of Cluster Science Kluwer Academic Publishers-Plenum Publishers 7/3(1996-09-01), 407-421 1040-7278 7:3<407 1996 7 10876 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer