Formation of cyanates in low-valent uranium chemistry: a synergistic experimental/theoretical study.
Computational studies on the reductive activation of a mixture of CO and NO by the U(iii) complex [U(η-C8H6{Si(i)Pr3-1,4}2)(η-Cp*)], which affords a mixture of [U(η-C8H6{Si(i)Pr3-1,4}2)(η-Cp*)]2(μ-OCN)21 and [U(η-C8H6{Si(i)Pr3-1,4}2)(η-Cp*)]2(μ-O) 2, show that the reaction proceeds via an initial attack of CO on a μ-η(2):η(2) coordinated NO, side-on bridged between two uranium centres. This leads to the formation of the bridging oxo complex 2 and the cyanate radical; coordination of the latter to the starting complex and dimerisation affords 1. The DFT studies also predict the existence of the monocyanate-bridged, mixed valence species [U(η-C8H6{Si(i)Pr3-1,4}2)(η-Cp*)]2(μ-OCN) 3, which has now been experimentally observed.
Université de Toulouse et CNRS, INSA, UPS, UMR 5215, LPCNO, 135 Avenue de Rangueil, F-31077 Toulouse, France. laurent.maron@irsamc.ups-tlse.fr.
Christos E
CE
Kefalidis
Alistair S P
AS
Frey
S Mark
SM
Roe
F Geoffrey N
FG
Cloke
Laurent
L
Maron