Reactions of alkynyl-ruthenium complexes with the ketene dithioacetal, (MeS)₂C═C(CN)₂
Date
2008
Authors
Armitt, D.
Bruce, M.
Skelton, B.
White, A.
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Journal article
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Organometallics, 2008; 27(14):3556-3563
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David J. Armitt, Michael I. Bruce, Brian W. Skelton and Allan H. White
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Abstract
Reactions of several alkynyl-ruthenium complexes with the ketene dithioacetal (MeS)<inf>2</inf>C=C(CN)<inf>2</inf> (2) are described. The first examples of metalated 6-alkylthio-6-azafulvenes, Ru(C=CRC-(SMe)=C(CN)C=N(SMe)) (PPh<inf>3</inf>)Cp [R = Ph (5a), Fc (5b)], were obtained from Ru(C≡CR)(PPh<inf>3</inf>)<inf>2</inf>Cp, while Ru(C≡CPh)(CO) (PPh<inf>3</inf>)Cp gave dienyl complexes Ru(C(SMe)=CPhC(SMe)=C(CN)<inf>2</inf> }(CO)-(PPh<inf>3</inf>)<inf>n</inf>Cp [n = 1 (8), 0 (9)]. Yields of the azafulvenes were increased under conditions conducive to radical formation. The reaction between 5 and Ru(C≡CC≡CPh)(PPh<inf>3</inf>)<inf>2</inf>Cp afforded the alkynyl-dienyl Ru{C(SMe)=C(C≡CPh)C(SMe)=C(CN) <inf>2</inf>)(PPh<inf>3</inf>)Cp (11) and the dienynyl Ru(C≡CC(SMe)=CPhC- (SMe)=C(CN)<inf>2</inf>}(PPh<inf>3</inf>)<inf>2</inf>Cp (12), formed by formal insertion of either C≡C triple bond into one C-S bond. The reaction of Ru(C≡CPh)(PPh<inf>3</inf>)<inf>2</inf>Cp with dimethyl 2,3-dicyanofumarate (3) afforded diastereomers of the η<sup>3</sup>-dienyl complex Ru (η<sup>3</sup>-C(CN)(CO<inf>2</inf>Me)CPhC=C(CN)(CO<inf>2</inf>Me)} (PPh<inf>3</inf>)Cp (13). XRD structural determinations of 5a, 8, 9, 11, and one diastereomer of 13 are reported. © 2008 American Chemical Society.
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Copyright © 2008 American Chemical Society