Highly reduced organometallics. XI. Formal derivatives of the tricarbonylmetallates (6-) of chromium, molybdenum and tungsten

Gary L. Rochfort, John E. Ellis

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Abstract

Reduction of W(CO)3(PMTA) (PMTA = 1,1,4,7,7-pentamethyldiethylenetriamine) by six equivalents of potassium metal in liquid ammonia provides an incompletely characterized highly reduced carbonyltungstate ion which reacts with several electrophiles to provide derivatives containing only tungsten tricarbonyl units. These include W(CO)3(NH3)3, [W3(CO)9(μ-OC2H5)(μ3-OC2H5)2]3-, HW(CO)3(SnPh3)32- and the unusual [(Ph3Sn)2{(Ph2Sn)2OEt}W(CO)3]-. The latter compound results from an unprecedented phenyl-tin cleavage in the reaction of triphenyltin chloride and the highly reduced carbonyltungstate ion. Triphenyltin derivatives of the unknown M(CO)36- (M = Cr, Mo and W) have also been prepared by reacting M(CO)3(SnPh3)33- with Brønsted acids and Ph3SnCl. From these reactions the previously unknown HM(CO)3(SnPh3)32- (M = Cr, Mo and W) and M(CO)3(Ph3Sn)42- (M = Mo and W) have been isolated and characterized. The latter are the first compounds containing more than three triphenyltin units attached to one transition metal.

Original languageEnglish (US)
Pages (from-to)265-276
Number of pages12
JournalJournal of Organometallic Chemistry
Volume250
Issue number1
DOIs
StatePublished - Jul 5 1983

Bibliographical note

Funding Information:
We thank the donors of the Petroleum Research Fund, administered by the American Chemical Society and the National Science Foundation (CHE 82-10496) for continuing support of this research.

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