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Facile Dinitrogen and Dioxygen Cleavage by a Uranium(III) Complex: Cooperativity Between the Non‐Innocent Ligand and the Uranium Center
Author(s) -
Wang Penglong,
Douair Iskander,
Zhao Yue,
Wang Shuao,
Zhu Jun,
Maron Laurent,
Zhu Congqing
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202012198
Subject(s) - uranium , chemistry , molecule , cleavage (geology) , bond cleavage , ammonia , ligand (biochemistry) , redox , cooperativity , inorganic chemistry , medicinal chemistry , catalysis , organic chemistry , materials science , receptor , biochemistry , fracture (geology) , metallurgy , composite material
Activation of dinitrogen (N 2 , 78 %) and dioxygen (O 2 , 21 %) has fascinated chemists and biochemists for decades. The industrial conversion of N 2 into ammonia requires extremely high temperatures and pressures. Herein we report the first example of N 2 and O 2 cleavage by a uranium complex, [N(CH 2 CH 2 NP i Pr 2 ) 3 U] 2 (TMEDA), under ambient conditions without an external reducing agent. The N 2 triple bond breaking implies a U III –P III six‐electron reduction. The hydrolysis of the N 2 reduction product allows the formation of ammonia or nitrogen‐containing organic compounds. The interaction between U III and P III in this molecule allows an eight‐electron reduction of two O 2 molecules. This study establishes that the combination of uranium and a low‐valent nonmetal is a promising strategy to achieve a full N 2 and O 2 cleavage under ambient conditions, which may aid the design of new systems for small molecules activation.