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学術論文

α-Radical Phosphines: Synthesis, Structure, and Reactivity

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Gu,  Lianghu
Research Group Alcarazo, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Zheng,  Yiying
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Haldón,  Estella
Research Group Alcarazo, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Goddard,  Richard
Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Thiel,  Walter
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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引用

Gu, L., Zheng, Y., Haldón, E., Goddard, R., Bill, E., Thiel, W., & Alcarazo, M. (2017). α-Radical Phosphines: Synthesis, Structure, and Reactivity. Angewandte Chemie International Edition, 56(30), 8790-8794. doi:10.1002/anie.201704185.


引用: https://hdl.handle.net/11858/00-001M-0000-002D-B299-A
要旨
A series of phosphines featuring a persistent radical were synthesized in two steps by condensation of dialkyl-/diarylchlorophosphines with stable cyclic (alkyl)(amino)carbenes (cAACs) followed by one-electron reduction of the corresponding cationic intermediates. Structural, spectroscopic, and computational data indicate that the spin density in these phosphines is mainly localized on the original carbene carbon from the cAAC fragment; thus, it remains in the α-position with respect to the central phosphorus atom. The potential of these α-radical phosphines to serve as spin-labeled ligands is demonstrated through the preparation of several AuI derivatives, which were also structurally characterized by single-crystal X-ray diffraction.