期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 21, 期 3, 页码 1184-1190出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201405356
关键词
carboranes; copper; cross-coupling; photocatalysis; UV; Vis spectroscopy
资金
- 973 Program [2013CB834800, 2013CB632403]
- Ministry of Science and Technology of China [2012DFH40090]
- NSFC [21102101, 21172173, 21273257, 21371175]
- Beijing Natural Science Foundation [2142033]
- Tianjin Normal University Foundation [5L105]
- CAS-Croucher
- Chinese Academy of Sciences [2013FFGB0009]
Four heteroleptic copper(I) complexes containing phenanthroline and monoanionic nido-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, -functionalized tertiary amines were obtained in good-to-excellent yields by light irradiation (>420nm) of a mixture of our Cu-I complex, 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 (O-2(-)) rather than singlet oxygen (O-1(2)) during these photocatalytic reactions.
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