Department of Chemistry, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States.
J Am Chem Soc. 2017 Mar 29;139(12):4246-4249. doi: 10.1021/jacs.6b13220. Epub 2017 Mar 16.
This Communication describes the photoredox catalysis of a C-C coupling reaction between 1-phenylpyrrolidine (PhPyr) and phenyl trans-styryl sulfone by visible-light-absorbing colloidal CdS quantum dots (QDs), without a sacrificial oxidant or reductant, and without a co-catalyst. Simple kinetic analysis reveals that photo-oxidation of PhPyr by the QDs is the rate-limiting step. Disordering of the ligand shell of the QDs by creating mixed monolayers of oleate and octylphosphonate increases the initial rate of the reaction by a factor of 2.3, and the energy efficiency (mol product/joule of incident photons) of the reaction by a factor of 1.6, by facilitating the hole-transfer step.
本通讯描述了可见光吸收胶体 CdS 量子点（QDs）在没有牺牲氧化剂或还原剂、也没有共催化剂的情况下，对 1-苯基吡咯烷（PhPyr）和苯基反式苯乙烯基砜之间的 C-C 偶联反应的光氧化还原催化作用。简单的动力学分析表明，QDs 对 PhPyr 的光氧化是速率限制步骤。通过油酸和辛基膦酸的混合单层来打乱 QDs 的配体壳，可以使反应的初始速率提高 2.3 倍，通过促进空穴转移步骤，使反应的能量效率（每焦耳入射光子的摩尔产物）提高 1.6 倍。
