期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 60, 期 12, 页码 6372-6376出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202014929
关键词
green light; iodide ligands; olefin metathesis; photopolymerization; sulfur-chelated ruthenium
A novel catalyst Ru-S-CF3-I was synthesized with distinct activity and selectivity profiles for olefin metathesis reactions. The combination of photoisomerization and photochemical release of chloride ions allows for a wide scope of photoinduced olefin metathesis reactions.
A trifluoromethyl sulfur-chelated ruthenium benzylidene, Ru-S-CF3-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-CF3-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-CF3-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.
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