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Article Abstract
In this work, we report the first example of the PCET reactivity for a boron cluster compound, the zwitterionic -carboranyl diphosphonium derivative 7-P(H)Bu-10-P(H)Pr--CBH. This main-group reagent efficiently transfers two electrons and two protons to quinones to yield hydroquinones and regenerate a neutral -carboranyl diphosphine, 1-PBu-2-PPr--CBH. As we have previously reported the conversion of this -carboranyl diphosphine into the zwitterionic derivative upon reaction with main group hydrides, the transformation reported herein represents a complete synthetic cycle for the metal-free reduction of quinones, with the redox-active carboranyl diphosphine scaffold acting as a mediator. The proposed mechanism of this reduction, based on p determination, electrochemical studies, and kinetic isotope effect determination, involves the electron transfer from the - cluster to the quinone coupled with the delivery of protons.
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Department of Chemistry and Biochemistry, University of South Carolina, 631 Sumter St, Columbia, South Carolina 29208, United States.
In this work, we report the first example of the PCET reactivity for a boron cluster compound, the zwitterionic -carboranyl diphosphonium derivative 7-P(H)Bu-10-P(H)Pr--CBH. This main-group reagent efficiently transfers two electrons and two protons to quinones to yield hydroquinones and regenerate a neutral -carboranyl diphosphine, 1-PBu-2-PPr--CBH. As we have previously reported the conversion of this -carboranyl diphosphine into the zwitterionic derivative upon reaction with main group hydrides, the transformation reported herein represents a complete synthetic cycle for the metal-free reduction of quinones, with the redox-active carboranyl diphosphine scaffold acting as a mediator.
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Department of Chemistry and Biochemistry, University of South Carolina, 631 Sumter Street, Columbia, South Carolina 29208, United States.
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