Latent ruthenium olefin metathesis catalysts featuring a phosphine or an N-heterocyclic carbene ligand

The synthesis and characterization of latent 18-electron ruthenium benzylidene complexes (PCy 3)(( κ N, O)-picolinate) 2RuCHPh ( 5) and (H 2IMes)(( κ N, O)-picolinate) 2RuCHPh ( 6) are described. Both complexes appear as two isomers. The ratio between the isomers is dependent on l-type ligand. The complexes are inactive in ring-closing metathesis and ring-opening metathesis polymerization reactions even at elevated temperatures in the absence of stimuli. Upon addition of HCl, complexes 5 and 6 become highly active in olefin metathesis reactions. The advantage of the latent catalysts is demonstrated in the ring-opening metathesis polymerization of dicyclopentadiene, where the latency of 6 assures adequate mixing of catalyst and monomer before initiation. Trapping experiments suggests that the acid converts the 18-electron complexes into their corresponding highly olefin metathesis active 14-electron benzylidenes. Completely latent 18-electron Ru benzylidene pre-catalysts have been prepared and appear as mixtures of two isomers. Upon addition of acid these pre-catalysts convert into their highly metathesis active 14-electron benzylidene complexes. The latent forms of catalyst can be fully mixed with monomer before initiation, which is demonstrated in the ring-opening metathesis polymerization DCPD. [Display omitted]