Oxidative dimerization of arylalkynyl-ruthenium complexes
Date
2011
Authors
Bruce, M.
Burgun, A.
Gendron, F.
Grelaud, G.
Halet, J.
Skelton, B.
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Journal article
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Organometallics, 2011; 30(10):2861-2868
Statement of Responsibility
Michael I. Bruce, Alexandre Burgun, Frédéric Gendron, Guillaume Grelaud, Jean-François Halet and Brian W. Skelton
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Abstract
Chemical oxidation of Ru(C≡CPh)(PPh<inf>3</inf>)<inf>2</inf>Cp with [FeCp<inf>2</inf>]PF<inf>6</inf> affords the binuclear cationic complexes [Cp(PPh<inf>3</inf>)<inf>2</inf>Ru{=C=CHC<inf>6</inf>H<inf>4</inf>CPh=C=} Ru(PPh<inf>3</inf>)<inf>2</inf>Cp](PF<inf>6</inf>)<inf>2</inf> (2) and [Cp(PPh<inf>3</inf>)<inf>2</inf>Ru{C≡C(C<inf>6</inf>H<inf>4</inf>)CPh=C=} Ru(PPh<inf>3</inf>)<inf>2</inf>Cp]PF<inf>6</inf> (3) by radical coupling at sites shown to be electron-rich by DFT studies, particularly involving the acetylide C<inf>β</inf> and Ph C<inf>para</inf> atoms and, to a lesser extent, the Cp carbon atoms. Complexes 2 and 3 are related by facile deprotonation/protonation reactions. When the 4-position of the Ph group is blocked, attack by C<inf>β</inf> upon the Cp group occurs to give the bis(vinylidene) [Ru{=C=C(C<inf>6</inf>H<inf>4</inf>Me-4)-η-C <inf>5</inf>H<inf>4</inf>[Ru(PPh<inf>3</inf>)<inf>2</inf>{=C=CH(C <inf>6</inf>H<inf>4</inf>Me-4)}(PPh<inf>3</inf>)<inf>2</inf>Cp]}](PF <inf>6</inf>)<inf>2</inf> (4), which can be deprotonated to give [Ru{=C=C(C <inf>6</inf>H<inf>4</inf>Me-4)-η-C<inf>5</inf>H<inf>4</inf>[Ru(PPh <inf>3</inf>)<inf>2</inf>{C≡C(C<inf>6</inf>H<inf>4</inf>Me-4)}(PPh <inf>3</inf>)<inf>2</inf>Cp]}]PF<inf>6</inf> (5). Complex 4 is rapidly oxidized during workup to form [Ru{=C=C(C<inf>6</inf>H<inf>4</inf>Me)-η-C <inf>5</inf>H<inf>4</inf>[Ru(CO)(PPh<inf>3</inf>)<inf>2</inf>]}(PPh <inf>3</inf>)<inf>2</inf>Cp](PF<inf>6</inf>)<inf>2</inf> (6). Single-crystal X-ray structure determinations of the salts 2, 3, and 6 are reported. © 2011 American Chemical Society.
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Copyright © 2011 American Chemical Society