Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity

• DOI: 10.3762/bjoc.11.158
• Publication Date: 2015-08-20T07:39:53Z
• Authors: Karolina Żukowska; Eva Pump; Aleksandra E Pazio; Krzysztof Woźniak; Luigi Cavallo; Christian Slugovc
• Keywords: Science; Q; Organic chemistry; DFT calculations; 01 natural sciences; Full Research Paper; 0104 chemical sciences; ring-opening metathesis polymerisation; QD241-441; ring closing metathesis; olefin metathesis; ruthenium; DFT calculations; olefin metathesis; ring closing metathesis;; ring-opening metathesis polymerisation; ruthenium; RING-CLOSING METATHESIS; INDENYLIDENE COMPLEXES; BENZYLIDENE COMPLEXES; LIGAND; POLYMERIZATION; INITIATORS; ISOMERIZATION; DECOMPOSITION; REACTOR; CARBENES

Two ruthenium olefin metathesis initiators featuring electronically modified quinoline-based chelating carbene ligands are introduced. Their reactivity in RCM and ROMP reactions was tested and the results were compared to those obtained with the parent unsubstituted compound. The studied complexes are very stable at high temperatures up to 140 °C. The placement of an electron-withdrawing functionality translates into an enhanced activity in RCM. While electronically modified precatalysts, which exist predominantly in the trans-dichloro configuration, gave mostly the RCM and a minor amount of the cycloisomerization product, the unmodified congener, which preferentially exists as its cis-dichloro isomer, shows a switched reactivity. The position of the equilibrium between the cis- and the trans-dichloro species was found to be the crucial factor governing the reactivity of the complexes.