偕二茂铁铜（I）配合物[Cu(dmp)(N^P)]BF4 用于光诱导原子转移自由基加成反应。
Heteroleptic copper(I) complexes [Cu(dmp)(N^P)]BF for photoinduced atom-transfer radical addition reactions.
机构信息
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, Jiangsu, People's Republic of China.
Faculty of Science and Technology, Charles Darwin University, Darwin, NT 0909, Australia.
出版信息
Dalton Trans. 2023 Jun 13;52(23):8142-8154. doi: 10.1039/d3dt00321c.
Earth-abundant copper(I) coordination complexes of an imine-phosphine and a diimine have been developed as visible-light photocatalysts. Reaction of [Cu(MeCN)]BF with hetero-bidentate phosphinopyrazole (phpz) ligand RRCHNPPh (R = R = H (1a); R = H, R = Me (1b); R = H, R = Ph (1c); R = R = Me (1d)) and 2,9-dimethyl-1,10-phenanthroline (dmp) gave four heteroleptic bis-chelate Cu(I) complexes [Cu(dmp)(RRCHNPPh)]BF (R = R = H (2a); R = H, R = Me (2b); R = H, R = Ph (2c); R = R = Me (2d)) with distorted tetrahedral geometries. Complexes 2a-2d exhibited broad absorption in the visible spectrum and could facilitate photochemical intermolecular atom-transfer radical addition reactions of CBr, or CClBr, CHI to styrenes in yields up to 91% and with a broad substrate scope. The absorption, emission, redox potential and photocatalytic activity were dependent on the substituents on the phpz ligand. Mechanistic studies supported an atom-transfer radical addition (ATRA) mechanism.
已开发出一种含有亚胺-膦和二亚胺的铜（I）配位配合物，作为可见光光催化剂。[Cu（MeCN）] BF 与杂双齿膦吡唑（phpz）配体 RRCHNPPh（R = R = H（1a）；R = H，R = Me（1b）；R = H，R = Ph（1c）；R = R = Me（1d））和 2,9-二甲基-1,10-菲咯啉（dmp）反应，得到四个异核双螯合 Cu（I）配合物[Cu（dmp）（RRCHNPPh）] BF（R = R = H（2a）；R = H，R = Me（2b）；R = H，R = Ph（2c）；R = R = Me（2d）），具有扭曲的四面体几何形状。配合物 2a-2d 在可见光谱中表现出宽吸收，可促进 CBr 或 CClBr、CHI 与苯乙烯的光化学分子间原子转移自由基加成反应，产率高达 91%，具有广泛的底物范围。吸收、发射、氧化还原电位和光催化活性取决于 phpz 配体上的取代基。机理研究支持原子转移自由基加成（ATRA）机理。
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