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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

Authors

  • Ludovic Castro,

    1. Université de Toulouse, INSA, UPS, LPCNO, 135 avenue de Rangueil, 31077 Toulouse and the CNRS, LPCNO UMR 5215, 31077 Toulouse (France)
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  • Prof. Dr. Laurent Maron

    Corresponding author
    1. Université de Toulouse, INSA, UPS, LPCNO, 135 avenue de Rangueil, 31077 Toulouse and the CNRS, LPCNO UMR 5215, 31077 Toulouse (France)
    • Université de Toulouse, INSA, UPS, LPCNO, 135 avenue de Rangueil, 31077 Toulouse and the CNRS, LPCNO UMR 5215, 31077 Toulouse (France)
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Abstract

The mechanisms of the reduction of four isoelectronic heteroallenes (CS2, COS, PhN3, and PhNCO) by trivalent uranium complex (MeC5H4)3U were determined by using DFT methods. The experimental formation of either the bimetallic CS2 and the PhNCO uranium(IV) adducts or the bimetallic sulfide complex (COS) and the monometallic uranium(V) phenylimide complex (PhN3) were rationalized. The formation of the products was explained by a unique reaction mechanism with a uranium(IV)-bridged heteroallene intermediate.

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