Long-Lived Excited States of Zwitterionic Copper(I) Complexes for Photoinduced Cross-Dehydrogenative Coupling Reactions
Long-Lived Excited States of Zwitterionic Copper(I) Complexes for Photoinduced Cross-Dehydrogenative Coupling Reactions
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用于光诱导交叉脱氢偶联反应的两性离子铜（I）配合物的长寿命激发态
DOI：
10.1002/chem.201405356
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
Che Chi-Ming
中科院分区：
文献类型：
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作者：
Wang Bin;Shelar Deepak Prakash;Han Xian-Zhu;Li Ting-Ting;Guan Xiangguo;Lu Wei;Liu Kun;Chen Yong;Fu Wen-Fu;Che Chi-Ming
合成了四种含邻二氮杂菲和一阴离子碳硼双膦配体的杂感铜(I)配合物，并用多种光谱技术和X-射线衍射对其结构进行了表征。这些配合物在可见光范围内表现出强烈的吸收，激发态寿命在微秒量级上。考察了它们在可见光诱导交叉脱氢偶联反应中的应用。初步研究表明，四种铜(I)络合物中的一种是以氧为氧化剂的光诱导氧化C--H功能化的有效催化剂。此外，在好氧条件下，通过我们的CuI络合物、叔胺和各种亲核试剂(硝基烷、丙酮或吲哚)的混合物的光照射(α>；420 nm)，以良好到优异的产率获得了CuI功能化的叔胺。电子顺磁共振测量提供了在这些光催化反应中形成超氧阴离子(O2−⋅)而不是单线态氧(1O2)的证据。
Four heteroleptic copper(I) complexes containing phenanthroline and monoanionicnido‐carborane‐diphosphine ligands have been prepared and structurally characterized by various spectroscopic techniques and X‐ray diffraction. These complexes exhibit intense absorptions in the visible range and excited‐state lifetimes on the microsecond scale. Their application in visible‐light‐induced cross‐dehydrogenative coupling reactions was investigated. Preliminary studies showed that one of the four copper(I) complexes is an efficient catalyst for photoinduced oxidative CH functionalization using oxygen as oxidant. Furthermore, α‐functionalized tertiary amines were obtained in good‐to‐excellent yields by light irradiation (λ>420 nm) of a mixture of our CuIcomplex, tertiary amines, and a variety of nucleophiles (nitroalkane, acetone, or indoles) under aerobic conditions. Electron paramagnetic resonance measurements provided evidence for the formation of superoxide radical anions (O2−⋅) rather than singlet oxygen (1O2) during these photocatalytic reactions.