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Reversible Dihydrogen Activation and Hydride Transfer by a Uranium Nitride Complex
Author(s) -
Falcone Marta,
Poon Lok Nga,
Fadaei Tirani Farzaneh,
Mazzanti Marinella
Publication year - 2018
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.201800203
Subject(s) - hydride , chemistry , formate , ammonia , nitride , acetonitrile , imide , cyanamide , uranium , cleavage (geology) , medicinal chemistry , inorganic chemistry , polymer chemistry , hydrogen , catalysis , materials science , organic chemistry , layer (electronics) , fracture (geology) , metallurgy , composite material
Cleavage of dihydrogen is an important step in the industrial and enzymatic transformation of N 2 into ammonia. The reversible cleavage of dihydrogen was achieved under mild conditions (room temperature and 1 atmosphere of H 2 ) by the molecular uranium nitride complex, [Cs{U(OSi(O t Bu) 3 ) 3 } 2 (μ‐N)] 1, leading to a rare hydride–imide bridged diuranium(IV) complex, [Cs{U(OSi(O t Bu) 3 ) 3 } 2 (μ‐H)(μ‐NH)], 2 that slowly releases H 2 under vacuum. This complex is highly reactive and quickly transfers hydride to acetonitrile and carbon dioxide at room temperature, affording the ketimide‐ and formate‐bridged U IV species [Cs{U(OSi(O t Bu) 3 ) 3 } 2 (μ‐NH)(μ‐CH 3 CHN)], 3 and [Cs{U(OSi(O t Bu) 3 ) 3 } 2 (μ‐HCOO)(μ‐NHCOO)], 4 .