MULTINUCLEAR METAL-CARBONYL ALKOXIDE AND ARYLOXIDE DERIVATIVES AS MODELS FOR METAL-CARBONYLS ADSORBED ON METAL-OXIDE SUPPORTS
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The synthesis and characterization of two tungsten carbonyl dimers containing bridging alkoxide or aryloxide ligands are described. The crystal and molecular structures of [PPN]2[W2(CO)8(OCH2CF3)2], 1, and [Et4N]3[W2(CO)6(OPh)3]CH3CN, 2, are reported and compared with the structures of tetranuclear tungsten derivatives previously described. The dimer 1 crystalizes in the triclinic space group P 1 with unit cell parameters a = 13.460(11) , b = 12.318(5) , c = 13.842(10) , = 82.73(5), = 59.11(5), = 80.09(5), V = 1938(2) 3, and Z = 1. The complex 2 crystalizes in the monoclinic space group P21/n with unit cell parameters a = 11.954(2) , b = 19.359(4) , c = 26.462(5) , = 102.50(16), V = 5979(2) 3, Z = 4. Molecular modeling software was utilized to construct a tetranuclear derivative from 1 similar to the structurally characterized [W(CO)3OH]44tetramer. The two tetramers were found to possess similar molecular parameters. This supports the contention that dimers of type 1 are the precursors of the tetramers. Comparisons of the tungsten alkoxides and aryloxides with the behavior of W(CO)6on alumina are provided. Copyright 1990 WILEYVCH Verlag GmbH & Co. KGaA, Weinheim
