Actinide-mediated catalytic addition of E-H bonds (E=N, P, S) to carbodiimides, isocyanates, and isothiocyanates

Isabell S R Karmel; Matthias Tamm; Moris S Eisen

doi:10.1002/anie.201502041

Actinide-mediated catalytic addition of E-H bonds (E=N, P, S) to carbodiimides, isocyanates, and isothiocyanates

Angew Chem Int Ed Engl. 2015 Oct 12;54(42):12422-5. doi: 10.1002/anie.201502041. Epub 2015 Jun 18.

Authors

Isabell S R Karmel¹, Matthias Tamm², Moris S Eisen³

Affiliations

¹ Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Technion City, 32000 (Israel).
² Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig (Germany).
³ Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Technion City, 32000 (Israel). chmoris@tx.technion.ac.il.

PMID: 26088527
DOI: 10.1002/anie.201502041

Abstract

Unprecedented catalytic reactivity of actinide coordination complexes toward heterocumulenes, such as carbodiimides, isocyanates, and isothiocyanates is reported. The mono(imidazolin-2-iminato) thorium(IV) complex [Th(Im(Dipp) N){N(SiMe3 )2 }3 ] (1) was applied as a precatalyst for the addition of EH (E=N, P, S) bonds to the YCX core (Y=R2 N; X=NR2 , O, S) of carbodiimides, isocyanates, and isothiocyanates. The respective insertion products were obtained in high yields under mild reaction conditions, with complex 1 displaying high tolerance toward functional groups and heteroatoms.

Keywords: actinide catalysis; carbodiimides; isocyanates; nucleophilic insertion; thioisocyanates.