Understanding the mechanism of direct visible-light-activated [2+2] cycloadditions mediated by Rh and Ir photocatalysts: combined computational and spectroscopic studies

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The mechanism of [2 + 2] cycloadditions activated by visible light and catalyzed by bis-cyclometalated Rh(iii) and Ir(iii) photocatalysts was investigated, combining density functional theory calculations and spectroscopic techniques. Experimental observations show that the Rh-based photocatalyst produces excellent yield and enantioselectivity whereas the Ir-photocatalyst yields racemates. Two different mechanistic features were found to compete with each other, namely the direct photoactivation of the catalyst-substrate complex and outer-sphere triplet energy transfer. Our integrated analysis suggests that the direct photocatalysis is the inner working of the Rh-catalyzed reaction, whereas the Ir catalyst serves as a triplet sensitizer that activates cycloaddition via an outer-sphere triplet excited state energy transfer mechanism.
Publisher
ROYAL SOC CHEMISTRY
Issue Date
2021-07
Language
English
Article Type
Article
Citation

CHEMICAL SCIENCE, v.12, no.28, pp.9673 - 9681

ISSN
2041-6520
DOI
10.1039/d1sc02745j
URI
http://hdl.handle.net/10203/286989
Appears in Collection
CH-Journal Papers(저널논문)
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