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Reactivity and Selectivity in Ruthenium Sulfur‐Chelated Diiodo Catalysts
Author(s) -
Nechmad Noy B.,
Kobernik Victoria,
Tarannam Naziha,
Phatake Ravindra,
Eivgi Or,
Kozuch Sebastian,
Lemcoff N. Gabriel
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202014929
Subject(s) - ruthenium , chemistry , reactivity (psychology) , metathesis , trifluoromethyl , salt metathesis reaction , selectivity , photoisomerization , dicyclopentadiene , photochemistry , olefin fiber , catalysis , combinatorial chemistry , organic chemistry , isomerization , polymer , polymerization , medicine , pathology , alternative medicine , alkyl
A trifluoromethyl sulfur‐chelated ruthenium benzylidene, Ru‐S‐CF 3 ‐I , was synthesized and characterized. This latent precatalyst provides a distinct activity and selectivity profiles for olefin metathesis reactions depending on the substrate. For example, 1,3‐divinyl‐hexahydropentalene derivatives were efficiently obtained by ring‐opening metathesis (ROM) of dicyclopentadiene (DCPD). Ru‐S‐CF 3 ‐I also presented a much more effective photoisomerization process from the inactive cis ‐diiodo to the active trans ‐diiodo configuration after exposure to 510 nm (green light), allowing for a wide scope of photoinduced olefin metathesis reactions. DFT calculations suggest a faster formation and enhanced stability of the active trans ‐diiodo species of Ru‐S‐CF 3 ‐I compared with Ru‐S‐Ph‐I , explaining its higher reactivity. In addition, the photochemical release of chloride anions by irradiation of Cl‐BODIPY in the presence of DCPD derivatives with diiodo Ru benzylidenes, led to in situ generation of chloride complexes, which quickly produced the corresponding cross‐linked polymers. Thus, novel selective pathways that use visible light to guide olefin metathesis based synthetic sequences is presented.