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DMSO molecule as ancillary ligand in Ru-based catalysts for ring opening metathesis polymerization

The ring-opening metathesis polymerization (ROMP) of norbornene (NBE) occurs in the presence of the fac-[RuCl2(S-DMSO)3(O-DMSO)] complex and ethyldiazoacetate (5 μL), where DMSO is S- or O-bonded dimethylsulfoxide. The yield is 62% (PDI = 1.64) at room temperature for 5 min and 88% (PDI = 1.93) at 50 ºC for 30 min, with [NBE]/[Ru] = 516 in CHCl3. The yield is 90% (PDI = 1.64) in the presence of NBu4ClO4 at room temperature for 5 min. The complex is practically inactive when one or two molecules of DMSO are replaced by pyridine, imidazole, 2-methyl-imidazole or benzimidazole. The in situ formation of the catalytic species and the behavior of the DMSO molecules as ancillary ligands in the reactivity of the RuII complexes are discussed.

olefin metathesis; ROMP; ancillary ligand; ruthenium; DMSO


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