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

S L Chatwin, M F Mahon, T J Prior, M K Whittlesey

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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.
LanguageEnglish
Pages625-632
Number of pages8
JournalInorganica Chimica Acta
Volume363
Issue number3
DOIs
StatusPublished - 15 Feb 2010

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Alkynes
carbenes
alkynes
Carbon Monoxide
hydrides
reactivity
chlorides
Hydrogen
hydrogen
imidazoles
Hydrides
marking
crystallography
deuterium
insertion
methylidyne
ligands
X ray crystallography
Deuterium
Chlorides

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Reactivity of the N-heterocyclic carbene complexes Ru(IMes)(2)(CO)HX (X = OH, Cl) with alkynes. / Chatwin, S L; Mahon, M F; Prior, T J; Whittlesey, M K.

In: Inorganica Chimica Acta, Vol. 363, No. 3, 15.02.2010, p. 625-632.

Research output: Contribution to journalArticle

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AB - 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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