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

doi:10.1002/anie.202014929

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

9 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 language	English
Pages (from-to)	6372-6376
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	12
DOIs	https://doi.org/10.1002/anie.202014929
State	Published - 15 Mar 2021

Keywords

green light
iodide ligands
olefin metathesis
photopolymerization
sulfur-chelated ruthenium

ASJC Scopus subject areas

Catalysis
Chemistry (all)

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10.1002/anie.202014929

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title = "Reactivity and Selectivity in Ruthenium Sulfur-Chelated Diiodo Catalysts",

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.",

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author = "Nechmad, {Noy B.} and Victoria Kobernik and Naziha Tarannam and Ravindra Phatake and Or Eivgi and Sebastian Kozuch and Lemcoff, {N. Gabriel}",

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AU - Nechmad, Noy B.

AU - Kobernik, Victoria

AU - Tarannam, Naziha

AU - Phatake, Ravindra

AU - Eivgi, Or

AU - Kozuch, Sebastian

AU - Lemcoff, N. Gabriel

PY - 2021/3/15

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N2 - 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.

AB - 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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KW - iodide ligands

KW - olefin metathesis

KW - photopolymerization

KW - sulfur-chelated ruthenium

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Reactivity and Selectivity in Ruthenium Sulfur-Chelated Diiodo Catalysts

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