Redistribution of trialkyl silanes catalyzed by iridium silyl complexes

Sehoon Park, Bong Gon Kim, Inigo Göttker-Schnetmann, Maurice Brookhart*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

31 Scopus citations

Abstract

[Ir(COE) 2Cl] 2 reacts with Et 3SiH at 23 °C to form a binuclear iridium complex (Et 3Si) 2(H) 2Ir(μ-Cl) 2Ir(H) 2(SiEt 3) 2, 1. Complex 1 reacts further with Et 3SiH at 60 °C to form a second binuclear iridium complex, Et 3Si(H) 2Ir(μ-SiEt 2) 2Ir(H) 2SiEt 3, 2, containing bridging Et 2Si groups. Activation of 2 with H 2 produces trace quantities of a very highly reactive but unobservable species which rapidly and efficiently catalyzes alkyl redistribution reactions of silanes, RR'R''SiH. D 2 and silane exchange experiments establish reactivity features of both 2 and the reactive intermediate. The intermediate cannot be observed, but it is likely a monomeric iridium silyl silylene complex that catalyzes alkyl scrambling via silane exchanges coupled with 1,3-alkyl migrations between silicon centers. DFT calculations support such a mechanism.

Original languageEnglish
Pages (from-to)307-316
Number of pages10
JournalACS Catalysis
Volume2
Issue number2
DOIs
StatePublished - 3 Feb 2012
Externally publishedYes

Keywords

  • 1,3-alkyl migration
  • bridged silylene complexes
  • H -triggered catalysis
  • iridium
  • low-T NMR spectroscopy
  • redistribution of silanes

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