Charge-separation in uranium diazomethane complexes leading to C-H activation and chemical transformation

J Am Chem Soc. 2008 Mar 5;130(9):2806-16. doi: 10.1021/ja0766472. Epub 2008 Feb 12.

Abstract

The reaction of diphenyldiazomethane with [((t-BuArO)3tacn)UIII] (1) results in an eta(2)-bound diphenyldiazomethane uranium complex. This complex exhibits unusual electronic properties as a charge-separated species with a radical anionic open-shell ligand, [((t-BuArO)3tacn)UIV(eta2-NNCPh2)] (2). Treating Ph2CN2 with a uranium complex that contains a sterically more demanding adamantane functionalized ligand, [((AdArO)3tacn)UIII] (3) results in an unprecedented C-H activation and nitrogen insertion to produce a five-membered heterocyclic indazole complex, [((AdArO)3tacn)UIV(eta(2)-3-phen(Ind))] (5). X-ray crystallography and spectroscopic characterization of these two compounds show that the [((t-BuArO)3tacn)UIV(eta(2)-NNCPh2)] compound is a U(IV) complex with a radical anionic ligand, whereas [((AdArO)3tacn)UIV(eta(2)-3-phen(Ind))] is a U(IV) f (2) species with a closed-shell ligand.

Publication types

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

MeSH terms

  • Crystallography, X-Ray
  • Diazomethane / chemistry*
  • Models, Molecular
  • Molecular Structure
  • Organometallic Compounds / chemical synthesis
  • Organometallic Compounds / chemistry*
  • Stereoisomerism
  • Temperature
  • Uranium / chemistry*

Substances

  • Organometallic Compounds
  • Uranium
  • Diazomethane