Photochemical nitrogenation of alkanes and arenes by a strongly luminescent osmium(VI) nitrido complex

Xiang, Jing1,2; Jin, Xin-Xin1; Su, Qian-Qian1; Cheng, Shun-Cheung2; Ko, Chi-Chiu2; Man, Wai-Lun3; Xue, Minying4,5; Wu, Liangliang6; Che, Chi-Ming4,5; Lau, Tai-Chu2

2019-03-29

10.1038/s42004-019-0142-3

Communications Chemistry   影响因子和分区

2399-3669

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, [Os-VI(N) (NO2-L) (CN)(3)](-) (NO2-OsN) with emission quantum yield (Phi) and life time (tau) of 3.0% and 0.48 mu s, 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 ON ligand to Os N charge transfer transitions, and as a result it possesses [Os = N-center dot] nitridyl character and is highly electrophilic.

ESCI ; SCI

英语

其他

Hong Kong University Grants Committee[AoE/P-03-08]

Chemistry

Chemistry, Multidisciplinary

WOS:000463163400001

NATURE PUBLISHING GROUP

Web of Science

1.Yangtze Univ, Coll Chem & Environm Engn, Jingzhou 434020, Hubei, Peoples R China;
2.City Univ Hong Kong, Dept Chem, Kowloon Tong, Tat Chee Ave, Hong Kong 999077, Peoples R China;
3.Hong Kong Baptist Univ, Dept Chem, Kowloon Tong, Hong Kong 999077, Peoples R China;
4.Univ Hong Kong, Dept Chem, Pokfulam, Pokfulam Rd, Hong Kong 999077, Peoples R China;
5.Univ Hong Kong, State Key Lab Synthet Chem, Pokfulam, Pokfulam Rd, Hong Kong 999077, Peoples R China;
6.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China

Xiang, Jing,Jin, Xin-Xin,Su, Qian-Qian,et al. Photochemical nitrogenation of alkanes and arenes by a strongly luminescent osmium(VI) nitrido complex[J]. Communications Chemistry,2019,2.

Xiang, Jing.,Jin, Xin-Xin.,Su, Qian-Qian.,Cheng, Shun-Cheung.,Ko, Chi-Chiu.,...&Lau, Tai-Chu.(2019).Photochemical nitrogenation of alkanes and arenes by a strongly luminescent osmium(VI) nitrido complex.Communications Chemistry,2.

Xiang, Jing,et al."Photochemical nitrogenation of alkanes and arenes by a strongly luminescent osmium(VI) nitrido complex".Communications Chemistry 2(2019).