ABSTRACT p ‐Tolyl(trimethylsilyl)diazomethane is a readily accessible and easy‐to‐handle net carbyne donor reagent. It reacts with ( p ‐cymene)RuCl 2 2 in MeCN to give the phosphine‐free chloride‐bridged dinuclear complex (MeCN) 2 RuCl 2 ( = C( p ‐tolyl)(SiMe 3 )) 2 ( 2 ) carrying a silyl group on each of the carbene ligands. Treatment of 2 with either PCy 3 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 d z2 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.
Cui et al. (2026) studied this question.