Synthesis and Reactivity of Ruthenium(BINAP)(PPh3)

Yifei Zhou, Niels H. Wensink, Anne Frédérique Pécharman, Fedor M. Miloserdov

Research output: Contribution to journalArticlepeer-review


Ru(BINAP)(PPh3)HCl cleanly reacts with LiCH2TMS to give Ru(BINAP)(PPh3) (1) that has been fully characterized, including by X-ray diffraction (BINAP and TMS stand for (2,2′-bis(diphenylphosphino)-1,1′-binaphthyl and trimethylsilyl respectively). In sharp contrast with other carbonyl-free phosphine complexes of Ru(0), 1 demonstrates a strikingly high thermal stability and no propensity for intramolecular C−H activation (cyclometalation). Yet 1 coordinates acetonitrile and readily exchanges its PPh3 ligand with alkenes and dienes, thus behaving like a “masked” 16-e Ru(0) species. Electron-poor alkenes coordinate more readily than electron-rich ones, which testifies for the nucleophilic character of the Ru(0)-BINAP fragment. While being thermally stable, 1 is highly reactive and is capable of activating C−H and N−H bonds, and even of cleaving an inert N−Et bond. The combination of high reactivity and stability originates from the P,arene-chelation by the BINAP ligand, i.e., the coordinated π-arene stabilizes Ru(0) to prevent cyclometalation, yet it can slide upon substrate coordination, thereby enabling a variety of inert bond activation reactions to occur under mild conditions.

Original languageEnglish
Article numbere202318684
JournalAngewandte Chemie - International Edition
Issue number14
Early online date29 Feb 2024
Publication statusPublished - 2 Apr 2024


  • C−N activation
  • Low-valent transition metal complexes
  • Ruthenium
  • Tethered arene ligands

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)


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