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Facile CO Cleavage by a Multimetallic CsU 2 Nitride Complex
Author(s) -
Falcone Marta,
Kefalidis Christos E.,
Scopelliti Rosario,
Maron Laurent,
Mazzanti Marinella
Publication year - 2016
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.201606796
Subject(s) - nitride , disproportionation , uranium , bond cleavage , chemistry , catalysis , cleavage (geology) , materials science , crystallography , inorganic chemistry , nanotechnology , organic chemistry , metallurgy , layer (electronics) , fracture (geology) , composite material
Uranium nitrides are important materials with potential for application as fuels for nuclear power generation, and as highly active catalysts. Molecular nitride compounds could provide important insight into the nature of the uranium–nitride bond, but currently little is known about their reactivity. In this study, we found that a complex containing a nitride bridging two uranium centers and a cesium cation readily cleaved the C≡O bond (one of the strongest bonds in nature) under ambient conditions. The product formed has a [CsU 2 (μ‐CN)(μ‐O)] core, thus indicating that the three cations cooperate to cleave CO. Moreover, the addition of MeOTf to the nitride complex led to an exceptional valence disproportionation of the CsU IV –N–U IV core to yield CsU III (OTf) and [MeN=U V ] fragments. The important role of multimetallic cooperativity in both reactions is illustrated by the computed reaction mechanisms.