Synthesis and reactions of the co-ordinatively unsaturated hexafluorobut-2-yne complex [WBr2(CO)(CF3C≡CCF3)2]. the crystal and molecular structure of [{W[C(CF3)=C(CF3)P(OEt)2O](μ-Br)(CO)(CF 3C≡CCF3)}2]

Jack L. Davidson, Giuseppe Vasapollo, John C. Millar, Kenneth W. Muir

Research output: Contribution to journalArticle

Abstract

Reaction of [{WBr2(CO)4}2] with CF3C=CCF3 in pentane affords the bis(alkyne) complex [WBr2(CO)(CF3C=CCF3)2] (1) in which the carbonyl ligand appears to function as a s-donor ligand only, according to i.r. data. Complex (1) reacts with P(OMe)3 and P(OEt)3 to give dimeric complexes [{W[C(CF3)=C(CF3)P(OR)2O](µ-Br)(CO)(CF 3C=CCF3)}2] containing a novel vinylphosphonate ligand resulting from a Michaelis-Arbuzov type elimination of alkyl bromide. The structure of the complex with R = Et has been determined by X-ray analysis. Four centrosymmetric molecules occupy a monoclinic cell with a = 24.068(2), b = 8.440(2), c = 25.197(2) Å, ß = 121.50(1)°, space group I2/a (no. 15, C2h6), and R = 0.036 for 2 872 reflections. The tungsten co-ordination is octahedral with mutually cis carbonyl and s-alkenyl carbon atoms both trans to µ-Br groups, and with phosphate O trans to a four-electron donor ?2-CF3C=CCF3. The bonding in the novel vinylphosphonate W[C(CF3)=C(CF3)P(OEt)2O] chelate ring is discussed.

Original languageEnglish
Pages (from-to)2165-2170
Number of pages6
JournalJournal of the Chemical Society, Dalton Transactions
Issue number9
DOIs
Publication statusPublished - 1987

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