Ring-opening and double-metallation reactions of the N-Heterocyclic carbene ligand in Cp∗(IXy)Ru (IXy = 1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene) complexes. Access to an anionic fischer-type carbene complex of ruthenium This paper is dedicated to John Bercaw on the occasion of his 70th birthday

Hsuch-Ju Liu*, Micah S. Ziegler, T. Don Tilley

*Corresponding author for this work

Research output: Contribution to journalArticle

9 Scopus citations

Abstract

An N-heterocylic carbene (NHC) ring-opening reaction was observed upon treatment of the silyl complex Cp(IXy-H)(H)RuSiH2Mes [1; IXy = 1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene; IXy-H = 1-(2-CH2C6H3-6-methyl)-3-(2,6-dimethylphenyl)imidazol-2-ylidene-1-yl (the deprotonated form of IXy); Cp = η5-C5Me5] with LiCH2SiMe3. This reaction results in formation of a novel, anionic Fischer-type carbene complex Cp(H)Ru{κ2-CHN(Xyl)CH[Si(CH2SiMe3)Mes]N(Xyl)Li} (4). This ring-opening reaction demonstrates a new pathway for NHC degradation via the cooperation of ruthenium, silicon, and lithium. Additionally, treatment of the dinitrogen complex Cp(IXy-H)Ru(N2) with LiCH2SiMe3 led to the doubly-metallated complex [Cp(IXy-2H)Ru]Li (5), which exhibits a solid-state polymeric structure and metallation of both xylyl groups of the IXy ligand. Finally, removal of a hydride from 4, achieved with two equiv of B(C6F5)3, led to C-H activation of the Cp ligand and formation of an unusual, formally dianionic η5-Me4C5CH2B(C6F5)3 ligand in a ruthenium carbene complex [η5-Me5C5CH2B(C6F5)3](H)Ru{κ3-CHN(Xyl)CH[SiH(CH2SiMe3)Mes]N(Xyl)} (7).

Original languageEnglish
Pages (from-to)203-208
Number of pages6
JournalPolyhedron
Volume84
DOIs
StatePublished - 14 Dec 2014

Keywords

  • Anionic carbene complexes C-H activation
  • Cyclometalation
  • N-heterocyclic carbene ring-opening
  • Silylene complexes

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