Facile CO Cleavage by a Multimetallic CsU2 Nitride Complex.
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 [CsU2 (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.
Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015, Lausanne, Switzerland.
Marta
M
Falcone
LPCNO,CNRS & INSA, UPS, Université de Toulouse, 135 Avenue de Rangueil, 31077, Toulouse, France.
Christos E
CE
Kefalidis
Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015, Lausanne, Switzerland.
Rosario
R
Scopelliti
LPCNO,CNRS & INSA, UPS, Université de Toulouse, 135 Avenue de Rangueil, 31077, Toulouse, France. laurent.maron@irsamc.ups-tlse.fr.
Laurent
L
Maron
Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015, Lausanne, Switzerland. marinella.mazzanti@epfl.ch.
Marinella
0000-0002-3427-008X
M
Mazzanti
carbon monoxide cleavage; cooperativity; nitrides; uranium; uranium disproportionation