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DOI: 10.1039/A803830I (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 3295-3300

Synthesis and characterisation of tungsten siloxides including the crystal structure of [WO{O(Ph2SiO)3}2(thf[hair space])]

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Brian J. Brisdon, Mary F. Mahon and Christopher C. Rainford

Abstract

Reactions of WOCl4 with NaOSiPh3 and Na2O2SiPh2 gave respectively [WO(Cl)(OSiPh3)3] and [{WO2[(OSiPh2)2O]}2]. Under similar conditions NaOSiPh3 reacted with [WO2Cl2(OSC4H8)2] to yield [WO2(OSiPh3)2(OSC4H8)2]. The novel spirocyclic tungstasiloxane [WO{O(Ph2SiO)3}2(thf[hair space])] was prepared from the reaction between equimolar quantities of (Ph2SiO)3 and WOCl4 in tetrahydrofuran. A crystal structure determination on this product revealed a distorted octahedral geometry about the central tungsten atom with the axially co-ordinated ether ligand trans to the oxo group, and puckered eight-membered siloxane rings oriented on opposite sides of the equatorial plane defined by the four co-ordinated siloxide O atoms. The W–O (Si) separations ranged from 1.851(7) to 1.896(8) Å and the W[double bond, length half m-dash]O bond length was 1.675(13) Å. In dichloromethane WCl6 reacted with (Ph2SiO)3 to afford good yields of WOCl4, whereas in tetrahydrofuran the same reactants caused solvent polymerisation.

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