Silane-isocyanide coupling involving 1,1-insertion of XylNC into the Si-H bond of a σ-silane ligand

Mark Lipke, T. Don Tilley

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

Complexes [PhBPPh3]RuH(η3-H 2SiRR′) (R,R′ = Me,Ph, 1a; RR′ = Ph2, 1b) react with XylNC (Xyl = 2,6-dimethylphenyl) to form Fischer carbene complexes [PhBPPh3]Ru(H)=[C(H)(N(Xyl)(η2-H- SiRR′))] (2a,b) that feature a γ-agostic Si-H bond. The ruthenium isocyanide complexes [PhBPPh3]Ru(H)(CNXyl) (η2-HSiHRR′) (6a,b) are not intermediates as they do not convert to 2a,b. Experimental and theoretical investigations indicate that XylNC is activated by initial coordination to the silicon center in 1a,b, followed by 1,1-insertion into an Si-H bond of the coordinated silane and then rearrangement to 2a,b.

Original languageEnglish (US)
Pages (from-to)10298-10301
Number of pages4
JournalJournal of the American Chemical Society
Volume135
Issue number28
DOIs
StatePublished - Jul 17 2013
Externally publishedYes

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Silanes
Ruthenium
Cyanides
Silicon
Ligands
carbene

All Science Journal Classification (ASJC) codes

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

Cite this

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title = "Silane-isocyanide coupling involving 1,1-insertion of XylNC into the Si-H bond of a σ-silane ligand",
abstract = "Complexes [PhBPPh3]RuH(η3-H 2SiRR′) (R,R′ = Me,Ph, 1a; RR′ = Ph2, 1b) react with XylNC (Xyl = 2,6-dimethylphenyl) to form Fischer carbene complexes [PhBPPh3]Ru(H)=[C(H)(N(Xyl)(η2-H- SiRR′))] (2a,b) that feature a γ-agostic Si-H bond. The ruthenium isocyanide complexes [PhBPPh3]Ru(H)(CNXyl) (η2-HSiHRR′) (6a,b) are not intermediates as they do not convert to 2a,b. Experimental and theoretical investigations indicate that XylNC is activated by initial coordination to the silicon center in 1a,b, followed by 1,1-insertion into an Si-H bond of the coordinated silane and then rearrangement to 2a,b.",
author = "Mark Lipke and Tilley, {T. Don}",
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Silane-isocyanide coupling involving 1,1-insertion of XylNC into the Si-H bond of a σ-silane ligand. / Lipke, Mark; Tilley, T. Don.

In: Journal of the American Chemical Society, Vol. 135, No. 28, 17.07.2013, p. 10298-10301.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Silane-isocyanide coupling involving 1,1-insertion of XylNC into the Si-H bond of a σ-silane ligand

AU - Lipke, Mark

AU - Tilley, T. Don

PY - 2013/7/17

Y1 - 2013/7/17

N2 - Complexes [PhBPPh3]RuH(η3-H 2SiRR′) (R,R′ = Me,Ph, 1a; RR′ = Ph2, 1b) react with XylNC (Xyl = 2,6-dimethylphenyl) to form Fischer carbene complexes [PhBPPh3]Ru(H)=[C(H)(N(Xyl)(η2-H- SiRR′))] (2a,b) that feature a γ-agostic Si-H bond. The ruthenium isocyanide complexes [PhBPPh3]Ru(H)(CNXyl) (η2-HSiHRR′) (6a,b) are not intermediates as they do not convert to 2a,b. Experimental and theoretical investigations indicate that XylNC is activated by initial coordination to the silicon center in 1a,b, followed by 1,1-insertion into an Si-H bond of the coordinated silane and then rearrangement to 2a,b.

AB - Complexes [PhBPPh3]RuH(η3-H 2SiRR′) (R,R′ = Me,Ph, 1a; RR′ = Ph2, 1b) react with XylNC (Xyl = 2,6-dimethylphenyl) to form Fischer carbene complexes [PhBPPh3]Ru(H)=[C(H)(N(Xyl)(η2-H- SiRR′))] (2a,b) that feature a γ-agostic Si-H bond. The ruthenium isocyanide complexes [PhBPPh3]Ru(H)(CNXyl) (η2-HSiHRR′) (6a,b) are not intermediates as they do not convert to 2a,b. Experimental and theoretical investigations indicate that XylNC is activated by initial coordination to the silicon center in 1a,b, followed by 1,1-insertion into an Si-H bond of the coordinated silane and then rearrangement to 2a,b.

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