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EnglishThe 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 cycloadditionviaan outer-sphere triplet excited state energy transfer mechanism.
| Titolo: | Understanding the mechanism of direct visible-light-activated [2 + 2] cycloadditions mediated by Rh and Ir photocatalysts: combined computational and spectroscopic studies | |
| Autore/i: | Jung H.; Hong M.; Marchini M.; Villa M.; Steinlandt P. S.; Huang X.; Hemming M.; Meggers E.; Ceroni P.; Park J.; Baik M. -H. | |
| Autore/i Unibo: | ||
| Anno: | 2021 | |
| Rivista: | ||
| Digital Object Identifier (DOI): | http://dx.doi.org/10.1039/d1sc02745j | |
| Abstract: | 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 cycloadditionviaan outer-sphere triplet excited state energy transfer mechanism. | |
| Data stato definitivo: | 2022-01-31T14:56:11Z | |
| Appare nelle tipologie: | 1.01 Articolo in rivista |
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