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Updated: Mar 6, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
A Convenient, Safe, and Atom-Economical Route to a Large Portfolio of Grubbs-Type Catalysts for Olefin Metathesis via
1Max-Planck-Institut für Kohlenforschung, Mülheim/Ruhr, Germany.
Abstract:
p-Tolyl(trimethylsilyl)diazomethane is a readily accessible and easy-to-handle net carbyne donor reagent. It reacts with [(p-cymene)RuCl2]2 in MeCN to give the phosphine-free chloride-bridged dinuclear complex [(MeCN)2RuCl2( = C(p-tolyl)(SiMe3))]2 (2) carrying a silyl group on each of the carbene ligands. Treatment of 2 with either PCy3 or an N-heterocyclic carbene (NHC) causes elimination of TMSCl with formation of the corresponding four-coordinate ruthenium alkylidynes. The non-bonding electron lone pair of significant dz2 character at their Ru center is prone to protonation; in this way, the alkylidyne unit is converted into a carbene ligand under very mild conditions. The sequence of alkylidyne formation/protonation opens a novel entry into all relevant "generations" of Grubbs and Grubbs-Hoveyda type catalysts, which is distinguished by a superior ligand- and atom economy, a good safety profile, and high overall yields. Moreover, the method is inherently flexible and arguably suitable for parallel screening and reaction optimization purposes.
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