TY - JOUR
T1 - Imposing Latency in Ruthenium Sulfoxide-Chelated Benzylidenes
T2 - Expanding Opportunities for Thermal and Photoactivation in Olefin Metathesis
AU - Segalovich-Gerendash, Gal
AU - Rozenberg, Illya
AU - Alassad, Nebal
AU - Nechmad, Noy B.
AU - Goldberg, Israel
AU - Kozuch, Sebastian
AU - Lemcoff, N. Gabriel
N1 - Publisher Copyright:
© 2020 American Chemical Society.
PY - 2020/4/17
Y1 - 2020/4/17
N2 - Herein we show the design and synthesis of an electron-rich, sulfoxide-chelated, ruthenium benzylidene. In contrast to previously reported sulfoxide-chelated ruthenium benzylidenes, this complex is more stable in a cis-dichloro conformation and is thus latent in typical olefin metathesis reactions. The complex was characterized by NMR, UV-vis, and X-ray spectroscopy, alongside density functional theory computations. The latent precatalyst could be activated thermally and, depending on the solvent, by UV-C or visible light. In addition, an original "thermo-chromatic" orthogonal sequence was developed, further improved by the use of a thioether chelated complex, where a divergent two-step synthesis can lead to a dihydrofuran or a dihydropyran depending only on the order by which the different stimuli, heat or light, are applied.
AB - Herein we show the design and synthesis of an electron-rich, sulfoxide-chelated, ruthenium benzylidene. In contrast to previously reported sulfoxide-chelated ruthenium benzylidenes, this complex is more stable in a cis-dichloro conformation and is thus latent in typical olefin metathesis reactions. The complex was characterized by NMR, UV-vis, and X-ray spectroscopy, alongside density functional theory computations. The latent precatalyst could be activated thermally and, depending on the solvent, by UV-C or visible light. In addition, an original "thermo-chromatic" orthogonal sequence was developed, further improved by the use of a thioether chelated complex, where a divergent two-step synthesis can lead to a dihydrofuran or a dihydropyran depending only on the order by which the different stimuli, heat or light, are applied.
KW - olefin metathesis
KW - photoinduced
KW - ruthenium
KW - sulfoxide
KW - sulfur-chelated
UR - http://www.scopus.com/inward/record.url?scp=85085126055&partnerID=8YFLogxK
U2 - 10.1021/acscatal.0c00676
DO - 10.1021/acscatal.0c00676
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AN - SCOPUS:85085126055
SN - 2155-5435
VL - 10
SP - 4827
EP - 4834
JO - ACS Catalysis
JF - ACS Catalysis
IS - 8
ER -