Chelating Ruthenium Phenolate Complexes: Synthesis, General Catalytic Activity, and Applications in Olefin Metathesis Polymerization

Abstract

Cyclic Ru-phenolates were synthesized, and these compounds were used as olefin metathesis catalysts. Investigation of their catalytic activity pointed out that, after activation with chemical agents, these catalysts promote ring-closing metathesis (RCM), enyne and cross-metathesis (CM) reactions, including butenolysis, with good results. Importantly, these latent catalysts are soluble in neat dicyclopentadiene (DCPD) and show good applicability in ring-opening metathesis polymeriyation (ROMP) of this monomer.

Ruthenium Amide Complexes – Synthesis and Catalytic Activity in Olefin Metathesis and in Ring‐Opening Polymerisation

“…Moreover, due to their latency and possibility of on‐demand activation, the Ru amide complexes can be used in ROMP of DCPD ( S8 ) and endo , exo ‐bicyclo[2.2.1]hept‐5‐ene‐2,3‐dicarboxylic acid ( S9 ). Although the best catalysts ( [Ru‐12] , [Ru‐18] and [Ru‐20] ) produced poly‐DCPD that showed reasonable results in mechanical tests, the low solubility of the new complexes in non‐polar solvents could restrict their commercial applications, as compared to the fully soluble LatMet catalyst family …”

“…Recently, we reported the synthesis of new ruthenium phenolate chelate complexes bearing altered anionic ligands (Figure , [Ru‐10] ) . These complexes exhibit almost no activity in metathesis reactions, but they can easily be switched on by adding Brønsted acids.…”

Société Chimique de France Prizes 2015

“…Grela and his research group are interested in synthesis, organometallic chemistry, and catalysis, including natural products, pharmaceutically relevant compounds, and catalysts for metathesis. He has reported in Chemistry—A European Journal on chelating ruthenium phenolate complexes 5. Grela is on the Editorial Board of Chemistry—A European Journal and the International Advisory Board of the European Journal of Organic Chemistry .…”

New aryloxybenzylidene ruthenium chelates – synthesis, reactivity and catalytic performance in ROMP

“…Phenoxybenzylidene complexes have been demonstrated to behave like latent catalysts in common testing reactions involving ring opening metathesis polymerisation (ROMP) of COD, norbornene derivative and dicyclopentadiene as well as cross metathesis (CM) of allylbenzene with Z -1,4-(diacetoxy)but-2-ene [9–10]. Although catalysts 1a – d are characterized by a number of advantages, they are not free from some weaknesses.…”

“…Although catalysts 1a – d are characterized by a number of advantages, they are not free from some weaknesses. They showed in some reactions a non-negligible catalytic activity in the absence of activators [9–10] and an instability of the activated forms. Herein, searching for improved latent catalysts that are less reactive in dormant form and highly active in the presence of an chemical activator, we report the synthesis and catalytic performance of new phenoxybenzylidene ruthenium chelates modified by introduction of electron donating and electron withdrawing substituents at the benzylidene ligand in para position to the coordinating oxygen and bearing instead of a strong sigma-donor ligand – tricyclohexylphosphine a weaker sigma-donor – a triphenylphosphine ligand or its derivatives.…”