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- Title
Photochemical nitrogenation of alkanes and arenes by a strongly luminescent osmium(VI) nitrido complex.
- Authors
Xiang, Jing; Jin, Xin-Xin; Su, Qian-Qian; Cheng, Shun-Cheung; Ko, Chi-Chiu; Man, Wai-Lun; Xue, Minying; Wu, Liangliang; Che, Chi-Ming; Lau, Tai-Chu
- Abstract
The search for a highly active nitrido complex that can transfer its nitrogen atom to inert organic molecules remains a challenge to chemists. In this regard, the use of solar energy to generate a reactive nitrido species is an appealing strategy to solve this problem. Here we report the design of a strongly luminescent osmium(VI) nitrido compound, [OsVI(N)(NO2-L)(CN)3]− (NO2-OsN) with emission quantum yield (Φ) and life time (τ) of 3.0% and 0.48 μs, respectively in dichloromethane solution. Upon irradiation with visible light, this complex readily activates the aliphatic C-H bonds of various hydrocarbons, including alkanes. The excited state of NO2-OsN can undergo ring-nitrogenation of arenes, including benzene. Photophysical and computational studies suggest that the excited state of NO2-OsN arises from O^N ligand to Os ≡ N charge transfer transitions, and as a result it possesses [Os = N•] nitridyl character and is highly electrophilic. Activation of C-H bonds through visible light irradiation remains a challenge in attaining energy efficient organic transformations. Here the authors show an osmium(VI) nitrido complex which can perform nitrogenation of cyclic alkanes and arenes by acting as a strong electrophile in the excited state.
- Subjects
ALKANES; OSMIUM; DICHLOROMETHANE; CHARGE transfer; VISIBLE spectra
- Publication
Communications Chemistry, 2019, Vol 2, Issue 1, pN.PAG
- ISSN
2399-3669
- Publication type
Article
- DOI
10.1038/s42004-019-0142-3