Insight into the reaction mechanisms of (MeC5H4)3U with isoelectronic heteroallenes CS2, COS, PhN3, and PhNCO by DFT studies: a unique pathway that involves bimetallic complexes

The mechanisms of the reduction of four isoelectronic heteroallenes (CS(2), COS, PhN(3), and PhNCO) by trivalent uranium complex (MeC(5)H(4))(3)U were determined by using DFT methods. The experimental formation of either the bimetallic CS(2) and the PhNCO uranium(IV) adducts or the bimetallic sulfide complex (COS) and the monometallic uranium(V) phenylimide complex (PhN(3)) were rationalized. The formation of the products was explained by a unique reaction mechanism with a uranium(IV)-bridged heteroallene intermediate.