Formation of an alpha-Diimine from Isocyanide Coupling Using Thorium(IV) and Uranium(IV) Phosphido-Methyl Complexes - INSA Toulouse - Institut National des Sciences Appliquées de Toulouse Access content directly
Journal Articles Organometallics Year : 2019

Formation of an alpha-Diimine from Isocyanide Coupling Using Thorium(IV) and Uranium(IV) Phosphido-Methyl Complexes

Abstract

To probe the reactivity of two potential sites at tetravalent thorium and uranium metal centers, we examined the monophosphido methyl complexes, (C5Me5)(2)An(CH3)[P(SiMe3)(Mes)], An = Th, U; Mes = 2,4,6-Me3C6H2. Reaction of these mixed ligand complexes with one, two, and three (or excess) equivalents of (BuNC)-Bu-t was explored. When (C5Me5)(2)An(CH3)[P(SiMe3)(Mes)] is treated with one equivalent of (BuNC)-Bu-t, the iminoacyl products, (C5Me5)(2)An[eta(2)-(BuN)-Bu-t=CCH3][P(SiMe3)(Mes)], are formed. Using three equivalents (or excess) of (BuNC)-Bu-t results in the formation of an alpha-diimine moiety, (C5Me5)(2)An[kappa(2)-(N,N)-N(Bu-t)C=CN(Bu-t)C=N(Bu-t)CH2]. When two equivalents of (BuNC)-Bu-t are added, only the mono-insertion or alpha-diimine was observed in a 3:1 ratio. Density functional theory calculations were carried out to determine the lowest energy pathway in the formation of the alpha-diimine product via the iminoacyl complex.
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Dates and versions

hal-04022184 , version 1 (09-03-2023)

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Pokpong Rungthanaphatsophon, Iker del Rosal, Robert J. Ward, Sean P. Vilanova, Steven P. Kelley, et al.. Formation of an alpha-Diimine from Isocyanide Coupling Using Thorium(IV) and Uranium(IV) Phosphido-Methyl Complexes. Organometallics, 2019, 38 (8), pp.1733-1740. ⟨10.1021/acs.organomet.9b00043⟩. ⟨hal-04022184⟩
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