A Photoswitchable Olefin Metathesis Catalyst

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• 作者：Aaron J. Teator ; Huiling Shao ; Gang Lu ; Peng LiuChristopher W. Bielawski
• 刊名：Organometallics
• 出版年：2017
• 出版时间：January 23, 2017
• 年：2017
• 卷：36
• 期：2
• 页码：490-497
• 全文大小：450K
• ISSN：1520-6041

文摘

A dithienylethene-functionalized N-heterocyclic carbene-Ru(II) complex was synthesized and found to undergo a reversible photoisomerization which influenced its intrinsic catalytic activity. UV-induced ring-closure enhanced the rate of ring-closing metathesis reactions (k_closed/k_opened = 1.4–1.7) and attenuated the rate of ring-opening metathesis polymerizations (k_closed/k_opened = 0.56–0.66). Visible light irradiation promoted cycloreversion and restored the initial activity. The ability to switch between the isomeric states of the catalyst was also utilized to modulate the rate of ongoing olefin metathesis reactions via photoirradiation. A computational investigation revealed how steric and electronic effects separately influence the transition states adopted by each form of the catalyst and afforded activation energies that were in agreement with the relative reaction rate constants determined by experiment.