A Thorium Chalcogenolate Series Generated by Atom Insertion into Thorium-Carbon Bonds

J Am Chem Soc. 2017 May 3;139(17):6261-6269. doi: 10.1021/jacs.7b02356. Epub 2017 Apr 21.

Abstract

A new thorium monoalkyl complex, Th(CH2SiMe3)(L3) (L = MeC(NiPr)2) (2), undergoes insertion of chalcogen atoms resulting in a series of thorium chalcogenolate complexes, Th(ECH2SiMe3)(L3) (E = S, SS, Se, Te; 5-8). Complex 6 represents the first alkyl disulfide thorium species and illustrates the ability of 2 to undergo controllable, stoichiometric atom insertion. All complexes have been characterized by 1H and 13C NMR spectroscopy, FTIR, EA, and melting point, and in the case of 1, 2, and 4-8, X-ray crystallography. Insertion was achieved by balancing the thermodynamic driving force of chalcogenolate formation versus the BDE of the pnictogen-chalcogen bond in the transfer reagent. Utilizing Me3NO as an oxygen atom transfer reagent led to C-H activation and SiMe4 extrusion rather than oxygen atom insertion, resulting in the alkoxide complex Th(OCH2NMe2)(L3) (4).

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Carbon / chemistry*
  • Chalcogens / chemical synthesis*
  • Chalcogens / chemistry
  • Crystallography, X-Ray
  • Models, Molecular
  • Molecular Conformation
  • Organometallic Compounds / chemical synthesis
  • Organometallic Compounds / chemistry*
  • Thermodynamics
  • Thorium Compounds / chemical synthesis*
  • Thorium Compounds / chemistry

Substances

  • Chalcogens
  • Organometallic Compounds
  • Thorium Compounds
  • Carbon