Reactivity of the N-heterocyclic carbene complexes Ru(IMes)(2)(CO)HX (X = OH, Cl) with alkynes

Reference:

Chatwin, S. L., Mahon, M. F., Prior, T. J. and Whittlesey, M. K., 2010. Reactivity of the N-heterocyclic carbene complexes Ru(IMes)(2)(CO)HX (X = OH, Cl) with alkynes. Inorganica Chimica Acta, 363 (3), pp. 625-632.

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Official URL:

http://dx.doi.org/10.1016/j.ica.2008.11.013

Abstract

Treatment of the 16-electron hydroxy hydride complex [Ru(IMes)(2)(CO)H(OH)] (1, IMes = 1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene) with HC CR affords the alkynyl species [Ru(IMes)(2)(CO) H(C CR)] (R = Ph 3, SiMe3, 4) and [Ru(IMes)(2)(CO)(C CR)(2)] (R = Ph, 5). Deuterium labelling studies show that the mono-alkynyl complexes are formed via hydrogen transfer from a coordinated alkyne ligand to Ru-OH, while bis-alkynyl formation is proposed to take place through hydrogen transfer to Ru-H. Both 3 and 5 readily coordinate CO to give the corresponding dicarbonyl species 6 and 7. Addition of HC CPh to the hydride chloride precursor [Ru(IMes)(2)(CO) HCl] (2) results in a different reaction pathway involving alkyne insertion into the Ru-H bond to yield the alkenyl chloride complex [Ru(IMes)(2)(CO)(CH=CHPh)Cl] 8. Complexes 3-8 have been structurally characterised by X-ray crystallography. (C) 2008 Elsevier B.V. All rights reserved.

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