Synthesis and reactivity of ruthenium phosphite indenylidene complexes

Xavier Bantreil, Albert Poater, César A. Urbina-Blanco, Yannick D. Bidal, Laura Falivene, Rebecca A.M. Randall, Luigi Cavallo, Alexandra M.Z. Slawin, Catherine S.J. Cazin*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

53 Scopus citations

Abstract

The synthesis of the four olefin metathesis precatalysts Caz-1a-d, featuring the NHC ligand N,N′-bis(2,4,6-trimethylphenyl)imidazolin-2- ylidene (SIMes) and four different phosphites (P(O iPr) 3, P(OPh) 3, P(OEt) 3, and P(OMe) 3), is reported. The complexes are readily synthesized from commercially available [RuCl 2(3-phenylinden-1-ylidene)(pyridine)(SIMes)] (Ind-III) in yields of up to 88%. These complexes adopt an unusual cis configuration between the phosphite and the NHC ligands. NMR experiments and computational studies confirm that the cis complexes are thermodynamically favored in comparison to their trans counterparts. In addition, the isomerization from trans to cis occurs via a mononuclear and non-dissociative mechanism. Among the four precatalysts, cis-Caz-1a, featuring a P(O iPr) 3 ligand, displays the highest activity in ring-closing metathesis and cross-metathesis transformations. Experiments at low catalyst loadings demonstrated the potential of this catalyst, allowing better conversions than with commonly used commercially available precatalysts.

Original languageEnglish (US)
Pages (from-to)7415-7426
Number of pages12
JournalOrganometallics
Volume31
Issue number21
DOIs
StatePublished - Nov 13 2012

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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