Triphenylbismuth seven-coordinate complexes of molybdenum(II) and tungsten(II) |
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| Authors: | Paul K. Baker Stuart G. Fraser Tony M. Matthews |
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| Affiliation: | aDepartment of Chemistry, University College of North Wales, Bangor, Gwynedd LL57 2UW, U.K. |
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| Abstract: | The seven-coordinate complexes [MI2(CO)3(NCMe)2] (M = Mo and W) react with one equivalent of BiPh3 in CH2Cl2 at room temperature to give the monoacetonitrile complexes [MI2(CO)3(NCMe)(BiPh3)]. The molybdenum complex [MoI2(CO)3(NCMe)(BiPh3)] after stirring in CH2Cl2 at room temperature for 5 h affords the iodide-bridged dimer [Mo(μ-I)I(CO)3(BiPh3)]2, whereas the tungsten complex [WI2(CO)3(NCMe)(BiPh3)] does not appear to dimerise even after stirring for 48 h in CH2Cl2 at room temperature. Reaction of [MI2(CO)3(NCMe)2] with two equivalents of BiPh3 gives the bistriphenylbismuth compounds [MI2(CO)3(BiPh3)2] in good yield. The new mixed ligand complexes [MI2(CO)3L(BiPh3)] were prepared either by reaction of [MI2(CO)3(NCMe)(BiPh3)]in situ with one equivalent of L(L = P(OPh)3), or an in situ reaction of [MI2(CO)3(NCMe)L] (L = PPh3 and SbPh3; and L = AsPh3 and PPh2Cy (for M = Mo only) with an equimolar quantity of BiPh3. Reaction of [MoI2(CO)3(NCMe)(BiPh3)] with one equivalent of 2,2′-bipyridyl (bipy) in CH2Cl2 at room temperature afforded the cationic complexes [MoI(CO)3(bipy)(BiPh3)]I in good yield. The complex [WI2(CO)3(NCMe)(BiPh3)] (prepared in situ) reacts with two equivalents of NaS2CNMe2·2H2O to eventually give the non-triphenylbismuth containing product [W(CO)3(S2CNMe2)2] in high yield. |
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