New seven-coordinate thiourea and N,N,N′,N′-tetramethylthiourea complexes of molybdenum(II) and tungsten(II) |
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| Authors: | Paul K Baker Stuart G Fraser |
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| Institution: | Department of Chemistry, University College of North Wales, Bangor, Gwynedd LL57 2UW, U.K. |
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| Abstract: | The compounds MI2(CO)3(NCMe)2] (M = Mo or W) react with one equivalent of thiourea (tu) in MeOH or N,N,N′,N′-tetramethylthiourea (tmtu) in CH2Cl2 at room temperature to initially afford the monoacetonitrile compounds MI2(CO)3(NCMe)L] (L = tu or tmtu) which rapidly transform to the isolated iodide bridged dimers, M(μ-I)I(CO)3L]2 with loss of acetonitrile. Reaction of WI2(CO)3(NCMe)2] with two equivalents of tu or tmtu gave the expected mononuclear seven-coordinate compounds WI2(CO)3L2]. However, reaction of MoI2(CO)3(NCMe)2] with two equivalents of tu or tmtu rapidly affords the iodide-bridged dimers Mo(μ-I)I(CO)2L2]2 with loss of carbon monoxide from MoI2(CO)3L2]. The low temperature (?70°C) 13C NMR spectrum of Mo(μ-I)I(CO)2 {SC(NMe2)2}2]2 suggests the complex is based on two capped octahedra with a carbonyl ligand capping each octahedral face. |
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