.png){kind=icon}
.png){kind=icon}
Return
Negatively charged cavity engineering in metal-organic clusters for efficient photocatalytic C–P coupling
.png){kind=icon}
OA
AI
D
W
H
B
Y
Y
DOI：10.1093/nsr/nwag467.png)
.png){kind=icon}
Original request for help.png){kind=icon}
Share.png){kind=icon}
Save
Abstract
En 中文
Photocatalytic cross-dehydrogenative C–P coupling is a promising and environmentally sustainable method for the synthesis of important phosphides. The development of effective photocatalysts capable of regulating the formation and release of reactive intermediates is crucial for enhancing the efficiency and selectivity of target products; but it remains an extremely challenging task. In this study, we designed and scale-up synthesized an atomically precise Co4 cluster photocatalyst with a well-defined negatively charged cavity that can be used to effectively stabilize cationic intermediates during a one-pot sequential C–P coupling reaction. This unique Co4 cluster enables the homogeneous synthesis of hydroxylated N-aryl-tetrahydroisoquinoline (N-aryl-THIQ) products with a yield as high as 99% through photothermal catalytic oxidation of molecular oxygen (O2). Subsequently, these hydroxylated products act as stable reservoirs for reactive iminium cation intermediates, which effectively promote the heterogeneous nucleophilic substitution reaction of equimolar substrates under non-illumination conditions, achieving THIQ phosphides with an optimized yield exceeding 95%. More importantly, the employed photocatalytic strategy ensures the quantitative recovery of Co4 through recrystallization and enables the preparation of phosphide products over 10-gram via cyclic reactions. The experimental results (co-crystal structure of the Co4 unit with the intermediate product, UV-vis titration, XPS, and ESR characterizations) combined with DFT calculations disclosed that the negatively charged cavity in the Co4 cluster is instrumental in mediating reactive species through electrostatic and π-conjugated interactions, resulting in hydroxylation and nucleophilic substitution reactions. This work pioneers the negatively charged cavity engineering in catalysts, which efficiently mediates cationic intermediates, thereby enabling highly efficient photocatalytic C–P coupling reactions.
Journal
IF:
17.1
Papers:
3.6K
Citations:
2.0W
Organization
Cited Papers