Reversible co-ordination of alkali metals to sulfur-based organometallic ligands [M(SC6F5)4(cp)]- (M = Mo or W, cp = η5-C5H5)

Jack L. Davidson, Calum H. McIntosh, Pascal C. Leverd, W. Edward Lindsell, Nigel J. Simpson

Research output: Contribution to journalArticle

Abstract

The photochemical reaction of Tl[Mo(SC6F5)2(CO)2(cp)] (cp = ?5-C5H5) with C6F5SSC6F5 in tetrahydrofuran (thf) solution affords the tetrathiolate Tl[Mo(SC6F5)4(cp)]. Similarly the photochemical reaction of [W(SC6F5)(CO)3(cp)] with 4 equivalents of Tl(SC6F5) gave Tl[W(SC6F5)4(cp)] in low yield. Reactions of [MI3(CO)2(cp)] (M = Mo or W) and [W(SC6F5)3(CO)(cp)] with M'(SC6F5) in thf solution gave the ionic derivatives Cs[Mo(SC6F5)4(cp)], M'[W(SC6F5)4(cp)] (M' = Cs, Rb or K) and the solvated derivatives [M'(thf)n][W(SC6F5)4(cp)] (M' = Li, n = 4; M' = Na, n = 1). Fluorine-19 NMR studies reveal fluxional behaviour involving the C6F5 groups in all the derivatives. Dynamic 133Cs and 19F NMR spectra of Cs[M(SC6F5)4(cp)] in addition show coupling between caesium and four of the ortho-fluorines of the SC6F5 groups, J(Cs-F) ˜ 58 Hz, at low temperatures providing evidence for reversible co-ordination between Cs+ and the organometallic anion.

Original languageEnglish
Pages (from-to)2423-2429
Number of pages7
JournalJournal of the Chemical Society, Dalton Transactions
Issue number16
DOIs
Publication statusPublished - 1994

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