Journal of the American Chemical Society, Vol.130, No.42, 13816-13817, 2008
Mechanistic studies on the reductive cyclooligomerisation of CO by U(III) mixed sandwich complexes; the molecular structure of [(U(eta-C8H6{(SiPr3)-Pr-i-1,4}(2))(eta-Cp*)](2)(mu-eta(1):eta(1)-C2O2)
The stoichiometric reaction of 1 equiv of CO with [(U(eta-C8H6{(SiPr3)-Pr-i-1,4}(2)) (eta-Cp-*)] affords the linear diuranium ynediolate complex [(U(eta-C8H6{(SiPr3)-Pr-i-1,4}(2)(eta-Cp-*)](2)(mu-eta(1):eta(1)-C2O2) which does not react with further CO to give the deltate derivative [(U(eta-C8H6{(SiPr3)-Pr-i-1,4}(2))(eta-Cp-*)](2)(mu-eta(1):eta(2)-C3O3). Spectroscopic and computational studies suggest a plausible mechanism for the formation of the deltate complex, in which a "zig-zag" diuranium ynediolate species is the key intermediate.