Actinide-Catalyzed Intermolecular Addition of Alcohols to Carbodiimides

Rami J. Batrice, Christos E. Kefalidis, Laurent Maron, Moris S. Eisen*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

27 Scopus citations

Abstract

The unprecedented actinide-catalyzed addition of alcohols to carbodiimides is presented. This represents a rare example of thorium-catalyzed transformations of an alcoholic substrate and the first example of uranium complexes showing catalytic reactivity with alcohols. Using the uranium and thorium amides U[N(SiMe3)2]3 and [(Me3Si)2N]2An[κ2-(N,C)-CH2Si(CH3)2N(SiMe3)] (An = Th or U), alcohol additions to unsaturated carbon-nitrogen bonds are achieved in short reaction times with excellent selectivities and high to excellent yields. Computational studies, supported by experimental thermodynamic data, suggest plausible models of the profile of the reaction which allow the system to overcome the high barrier of scission of the actinide-oxygen bond. Accompanied by experimentally determined kinetic parameters, a plausible mechanism is proposed for the catalytic cycle.

Original languageEnglish
Pages (from-to)2114-2117
Number of pages4
JournalJournal of the American Chemical Society
Volume138
Issue number7
DOIs
StatePublished - 2 Mar 2016
Externally publishedYes

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