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

Jing Xiang; Xin Xin Jin; Qian Qian Su; Shun Cheung Cheng; Chi Chiu Ko; Wai Lun MAN; Minying Xue; Liangliang Wu; Chi Ming Che; Tai Chu Lau

doi:10.1038/s42004-019-0142-3

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

Jing Xiang
, Xin Xin Jin
, Qian Qian Su
, Shun Cheung Cheng
, Chi Chiu Ko
, Wai Lun MAN
, Minying Xue
, Liangliang Wu
, Chi Ming Che
, Tai Chu Lau^*

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Journal article › peer-review

29 Citations (Scopus)

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, [Os^VI(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.

Original language	English
Article number	40
Number of pages	11
Journal	Communications Chemistry
Volume	2
Issue number	1
DOIs	https://doi.org/10.1038/s42004-019-0142-3
Publication status	Published - Dec 2019

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

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\textasciicircum{}N ligand to Os ≡ N charge transfer transitions, and as a result it possesses [Os = N•] nitridyl character and is highly electrophilic.",

author = "Jing Xiang and Jin, \{Xin Xin\} and Su, \{Qian Qian\} and Cheng, \{Shun Cheung\} and Ko, \{Chi Chiu\} and MAN, \{Wai Lun\} and Minying Xue and Liangliang Wu and Che, \{Chi Ming\} and Lau, \{Tai Chu\}",

note = "Funding Information: This work was supported by the National Natural Science Foundation of China (21771026), Hubei Provincial Natural Science Foundation of China (2018CFA047), the Research Grants Council of Hong Kong (CityU 11302917) and the Hong Kong University Grants Committee (AoE/P-03–08).",

year = "2019",

month = dec,

doi = "10.1038/s42004-019-0142-3",

language = "English",

volume = "2",

journal = "Communications Chemistry",

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publisher = "Springer Nature",

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TY - JOUR

T1 - Photochemical nitrogenation of alkanes and arenes by a strongly luminescent osmium(VI) nitrido complex

AU - Xiang, Jing

AU - Jin, Xin Xin

AU - Su, Qian Qian

AU - Cheng, Shun Cheung

AU - Ko, Chi Chiu

AU - MAN, Wai Lun

AU - Xue, Minying

AU - Wu, Liangliang

AU - Che, Chi Ming

AU - Lau, Tai Chu

N1 - Funding Information: This work was supported by the National Natural Science Foundation of China (21771026), Hubei Provincial Natural Science Foundation of China (2018CFA047), the Research Grants Council of Hong Kong (CityU 11302917) and the Hong Kong University Grants Committee (AoE/P-03–08).

PY - 2019/12

Y1 - 2019/12

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/85071172503

U2 - 10.1038/s42004-019-0142-3

DO - 10.1038/s42004-019-0142-3

M3 - Journal article

AN - SCOPUS:85071172503

SN - 2399-3669

VL - 2

JO - Communications Chemistry

JF - Communications Chemistry

IS - 1

M1 - 40

ER -

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

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