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Cyanoacetylenes and cyanoacetylides : versatile ligands in organometallic chemistry.

Cordiner, R. L. and Corcoran, D. and Yufit, D. S. and Goeta, A. E. and Howard, J. A. K. and Low, P. J. (2003) 'Cyanoacetylenes and cyanoacetylides : versatile ligands in organometallic chemistry.', Dalton transactions., 18 . pp. 3541-3549.


The nitrile like lone pair of the cyanoacetylene PhCequivalent toCCequivalent toN (1) has been found to coordinate readily to the Ru(PPh3)(2)Cp fragment, to give [Ru(Nequivalent toCCequivalent toCPh)(PPh3)(2)Cp]PF6 (2) which may be considered its an "extended" derivative of the more common benzonitrile complex [Ru(Nequivalent toCPh)(PPh3)(2)Cp]PF6 (3). Reaction of 1 with [Co-2(CO)(6)(dppm)] readily forms the mu,eta(2) complex [Co-2(mu,eta(2)-PhC(2)Cequivalent toN)(CO)(4)(dppm)] (4), which reacts with [RuCl(PPh3)(2)Cp] to give the mixed metal species [{Co-2(mu,eta(2)-PhC(2)Cequivalent toN) {Ru(PPh3)(2)Cp}(CO)(4)(mu-dppm)}]PF6 (5). The eta(1)(N) bonded PhCequivalent toCCequivalent toN ligand is labile, being displaced by NCMe at ambient temperature to afford [Ru(NCMe)(PPh3)(2)Cp]PF6, or by tcne to give trans-[{Ru(PPh3)(2)Cp}(2)(mu-tcne)}][PF6](2) (9). The metallocyanoacetylide [Ru(Cequivalent toCCequivalent toN)(PPh3)(2)Cp] (6) was prepared by lithiation (BuLi) of [Ru(Cequivalent toCH)(PPh3)(2)Cp] followed by treatment with PhOCN. Coordination of the metal fragments Ru(PPh3)(2)Cp or Fe(dppe)Cp to the N terminus in 6 occurs readily to give the homo- or hetero-bimetallic cations [{Cp(PPh3)(2)Ru}(mu-Cequivalent toCCequivalent toN){ML2Cp}](+), which were isolated as the PF6 salts [ML2Cp=Ru(PPh3)(2)Cp (7); Fe(dppe)Cp (8)]. The crystal structures of 2-5, 7 and 9 are reported. The electrochemical response of these complexes suggests there are considerable electronic interactions between the heterometallic end-caps in 8 through the polarised C3N bridge.

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Record Created:26 Apr 2007
Last Modified:20 Nov 2014 10:55

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