Reactivity and Selectivity in Ruthenium Sulfur-Chelated Diiodo Catalysts

Noy B. Nechmad, Victoria Kobernik, Naziha Tarannam, Ravindra Phatake, Or Eivgi, Sebastian Kozuch, N. Gabriel Lemcoff

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

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.

Original languageEnglish
Pages (from-to)6372-6376
Number of pages5
JournalAngewandte Chemie - International Edition
Volume60
Issue number12
DOIs
StatePublished - 15 Mar 2021

Keywords

  • green light
  • iodide ligands
  • olefin metathesis
  • photopolymerization
  • sulfur-chelated ruthenium

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