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Coupling of terminal alkynes by RuHXL(2) (X = Cl or N(SiMe(3))(2), L = P(i)Pr(3))

Author:
Lee, Joo-Ho  Caulton, Kenneth G.  


Journal:
JOURNAL OF ORGANOMETALLIC CHEMISTRY


Issue Date:
2008


Abstract(summary):

The compounds RuL(2)HX, where L = P(i)Pr(3) and X = Cl or N(SiMe(3))(2), are catalyst precursors for dimerization of terminal alkynes to enynes and also to cumulenes at 23 degrees C; selectivity among these products is X-dependent, but not high. Conversion of Ru species onto the catalytic cycle was undetectably small, so alternative approaches to understanding the catalytic mechanism were employed: stoichiometric reactions, independent synthesis of candidate intermediates, and trapping with CO. These show the intermediacy of vinylidenes and vinyl compounds, and reveal conversion of cumulenes to the thermodynamically more stable enynes. (C) 2007 Elsevier B.V. All rights reserved.


Page:
1664---1673


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