Activation of nitriles by metal ligand cooperation. reversible formation of ketimido- and enamido-rhenium PNP pincer complexes and relevance to catalytic design

Matthias Vogt, Alexander Nerush, Mark A. Iron, Gregory Leitus, Yael Diskin-Posner, Linda J W Shimon, Yehoshoa Ben-David, David Milstein

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The dearomatized complex cis-[Re(PNPtBu*)(CO)2] (4) undergoes cooperative activation of Cî - N triple bonds of nitriles via [1,3]-addition. Reversible C-C and Re-N bond formation in 4 was investigated in a combined experimental and computational study. The reversible formation of the ketimido complexes (5-7) was observed. When nitriles bearing an alpha methylene group are used, reversible formation of the enamido complexes (8 and 9) takes place. The reversibility of the activation of the nitriles in the resulting ketimido compounds was demonstrated by the displacement of p-CF 3-benzonitrile from cis-[Re(PNPtBu-N=CPh pCF3)(CO)2] (6) upon addition of an excess of benzonitrile and by the temperature-dependent [1,3]-addition of pivalonitrile to complex 4. The reversible binding of the nitrile in the enamido compound cis-[Re(PNP tBu-HNC=CHPh)(CO)2] (9) was demonstrated via the displacement of benzyl cyanide from 9 by CO. Computational studies suggest a stepwise activation of the nitriles by 4, with remarkably low activation barriers, involving precoordination of the nitrile group to the Re(I) center. The enamido complex 9 reacts via β-carbon methylation to give the primary imino complex cis-[Re(PNPtBu-HN=CC(Me)Ph)(CO)2]OTf 11. Upon deprotonation of 11 and subsequent addition of benzyl cyanide, complex 9 is regenerated and the monomethylation product 2-phenylpropanenitrile is released. Complexes 4 and 9 were found to catalyze the Michael addition of benzyl cyanide derivatives to α,β-unsaturated esters and carbonyls.

Original languageEnglish
Pages (from-to)17004-17018
Number of pages15
JournalJournal of the American Chemical Society
Issue number45
Publication statusPublished - Nov 13 2013


ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

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