The U=C double bond: synthesis and study of uranium nucleophilic carbene complexes

Thibault Cantat; Thérèse Arliguie; Anne Noël; Pierre Thuéry; Michel Ephritikhine; Pascal Le Floch; Nicolas Mézailles

doi:10.1021/ja807282s

The U=C double bond: synthesis and study of uranium nucleophilic carbene complexes

J Am Chem Soc. 2009 Jan 28;131(3):963-72. doi: 10.1021/ja807282s.

Authors

Thibault Cantat¹, Thérèse Arliguie, Anne Noël, Pierre Thuéry, Michel Ephritikhine, Pascal Le Floch, Nicolas Mézailles

Affiliation

¹ Laboratoire Heteroelements et Coordination, CNRS UMR 7653, Ecole Polytechnique, 91128, Palaiseau Cedex, France.

PMID: 19154173
DOI: 10.1021/ja807282s

Abstract

Treatment of U(BH(4))(4) with 1 or 3 equiv of Li(2)(SCS) x 1.5 Et(2)O, 1, afforded the actinide carbene complexes U(mu-SCS)(3)[U(BH(4))(3)](2) (4) and U(mu-SCS)(3)[Li(Et(2)O)](2) (6), respectively [SCS = (Ph(2)P = S)(2)C]. In THF, complex 4 was transformed into the mononuclear derivative (SCS)U(BH(4))(2)(THF)(2) (5). The multiple bond character of the uranium-carbon bond was first revealed by the X-ray crystal structures of the three complexes. The U=C bond in these complexes present a nucleophilic character, as shown by their reaction with a carbonyl derivative. Finally, DFT calculations prove the involvement of both 5f and 6d orbitals in both the sigma and the pi U-C bonds.