Polyhetero-ferrocenes and -ruthenocenes derived from the 1,4,2-diphosphastibolyl ring anion [P2SbC2But2]-

Steven J. Black, Matthew D. Francis, Cameron Jones

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Abstract

The complex [RuCl2(PPh3)3] reacted with the 1,4,2-diphosphastibolyl ring anion [P2SbC2But2]- (containing ca. 25% of the 1,2,4-triphospholyl anion [P3C2But2]-) to produce a cocrystallised mixture (crystal structure) of two isomers of [Ru(η5-P2SbC2But 2)2] with [Ru(η5-P2SbC2But2)]. Variable-temperature 31P-{1H} NMR studies on the mixture show one of the isomers and the last complex to be fluxional at room temperature. It is believed that an interring Sb ⋯ Sb interaction in the other isomer restricts its fluxionality in solution. The reaction of [P2SbC2But2]- with FeCl2 yielded only one isomer of the heteroferrocene complex [Fe(η5-P2SbC2But 2)2] which is also non-fluxional in solution and has a similar oxidation potential to that of ferrocene itself. The heteroruthenocene complexes [Ru(η5-P2SbC2But 2)(η5-C5R5)] (R = H or Me) were prepared by treating [Ru(η5-C5R5)(MeCN)3][PF 6] (R = H or Me) with [P2SbC2But2]-. The analogous ferrocene complex [Fe(η5-P2SbC2But 2)-(η5-C5Me5)] (crystal structure) was synthesized by treating a 1:1 mixture of [P2SbC2But2]- and Li(C5Me5) with half an equivalent of FeCl2. Treatment of [M(η5-P2SbC2But 2)(η5-C5Me5)] (M = Ru or Fe) with [W(CO)5(thf)] (thf = tetrahydrofuran) formed the secondary co-ordination complexes [M(η5-P2SbC2But 2)(η5-C5Me5){W(CO)5}] (M = Ru or Fe) in which the W(CO)5 fragment is η1 ligated to the phosphorus centre adjacent to the ring antimony centre. A diphosphastibolyl-bridged cationic triple-decker complex [(η5-C5Me5)Ru(μ-η 55-P2SbC2But 2)Ru(η5-C5Me5)][PF6] was the product of the reaction of [P2SbC2But2]- with 2 equivalents of [Ru(η5-C5Me5)(MeCN)3][PF 6].

Original languageEnglish
Pages (from-to)2183-2190
Number of pages8
JournalDalton
Issue number12
DOIs
Publication statusPublished - 21 Jun 1997
Externally publishedYes

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