Controlling the steric environment in U(η8-C8H6(1,4-SiR3)2)(η5-Cp*)] enables selective formation of either mononuclear U(v) or dinuclear U(iv) oxo and nitrido complexes.

ABSTRACT:The new dianionic ligand, C6H4{p-C(CH3)2C6H2Me2O −

Improving our comprehension of diverse CO2 activation pathways is of vital importance for the widespread future utilization of this abundant greenhouse gas. CO2 activation by uranium(III) complexes is now relatively well understood, with oxo/carbonate formation predominating as CO2 is readily reduced to CO, but isolated thorium(III) CO2 activation is unprecedented. We show that the thorium(III) complex, [Th(Cp′′)3] (1, Cp′′={C5H3(SiMe3)2‐1,3}), reacts with CO2 to give the mixed oxalate‐carboxylate thorium(IV) complex [{Th(Cp′′)2[κ2‐O2C{C5H3‐3,3′‐(SiMe3)2}]}2(μ‐κ2:κ2‐C2O4)] (3). The concomitant formation of oxalate and carboxylate is unique for CO2 activation, as in previous examples either reduction or insertion is favored to yield a single product. Therefore, thorium(III) CO2 activation can differ from better understood uranium(III) chemistry.

ThIV/ThIII reduction wave in the cyclic voltammogram of [Th(η-C5H3{SiMe3}2)3Cl].