Activation of carbon dioxide by new mixed sandwich uranium(III) complexes incorporating cyclooctatetraenyl and pyrrolide, phospholide, or arsolide ligands

作者：Kahan Rachel J; Cloke F Geoffrey N^*; Roe S Mark; Nief Francois

来源：New Journal of Chemistry, 2015, 39(10): 7602-7607.

DOI：10.1039/c5nj00590f

A series of uranium(III) mixed-sandwich complexes of the type [U(COTTIPS2)(Cp-EMe4)] (Cp-EMe4 = EC4Me4, E is N, P or As, and COTTIPS2 = C8H6{1,4-(SiPr3)-Pr-i}), featuring a heterocyclic five membered ring, have been synthesised and their X-ray crystal structures determined. The redox properties of these complexes have been assessed using cyclic voltammetry and the results compared to the purely carbocyclic mixed-sandwich analogues. The reactions of [U(COTTIPS2)(Cp-NMe4)] and [U(COTTIPS2)(Cp-PMe4)] with CO2 afford the structurally characterised carbamate and phosphacarbonate complexes [U(COTTIPS2)](2)(mu-O)(mu-eta(1):eta(1)-O2CEC4Me4)(2) (E = N and P respectively), arising from CO2 reduction and insertion.

• 出版日期2015