Bis(imino)pyridine cobalt-catalyzed dehydrogenative silylation of alkenes: Scope, mechanism, and origins of selective allylsilane formation

Crisita Carmen Hojilla Atienza, Tianning Diao, Keith J. Weller, Susan A. Nye, Kenrick M. Lewis, Johannes G.P. Delis, Julie L. Boyer, Aroop K. Roy, Paul J. Chirik

Research output: Contribution to journalArticlepeer-review

125 Scopus citations

Abstract

The aryl-substituted bis(imino)pyridine cobalt methyl complex, ( MesPDI)CoCH3 (MesPDI = 2,6-(2,4,6-Me 3C6H2-N=CMe)2C5H 3N), promotes the catalytic dehydrogenative silylation of linear α-olefins to selectively form the corresponding allylsilanes with commercially relevant tertiary silanes such as (Me3SiO) 2MeSiH and (EtO)3SiH. Dehydrogenative silylation of internal olefins such as cis- and trans-4-octene also exclusively produces the allylsilane with the silicon located at the terminus of the hydrocarbon chain, resulting in a highly selective base-metal-catalyzed method for the remote functionalization of C-H bonds with retention of unsaturation. The cobalt-catalyzed reactions also enable inexpensive α-olefins to serve as functional equivalents of the more valuable α, ω-dienes and offer a unique method for the cross-linking of silicone fluids with well-defined carbon spacers. Stoichiometric experiments and deuterium labeling studies support activation of the cobalt alkyl precursor to form a putative cobalt silyl, which undergoes 2,1-insertion of the alkene followed by selective β-hydrogen elimination from the carbon distal from the large tertiary silyl group and accounts for the observed selectivity for allylsilane formation.

Original languageEnglish (US)
Pages (from-to)12108-12118
Number of pages11
JournalJournal of the American Chemical Society
Volume136
Issue number34
DOIs
StatePublished - Jan 1 2014

All Science Journal Classification (ASJC) codes

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

Fingerprint Dive into the research topics of 'Bis(imino)pyridine cobalt-catalyzed dehydrogenative silylation of alkenes: Scope, mechanism, and origins of selective allylsilane formation'. Together they form a unique fingerprint.

Cite this