Skip to main content
eScholarship
Open Access Publications from the University of California

Synthesis, structure, and reactivity of crystalline molecular complexes of the {[C5H3(SiMe3)2]3Th}1-anion containing thorium in the formal +2 oxidation state

  • Author(s): Langeslay, RR
  • Fieser, ME
  • Ziller, JW
  • Furche, F
  • Evans, WJ
  • et al.
Abstract

© The Royal Society of Chemistry 2015. Reduction of the Th3+complex Cp′′3Th, 1 [Cp′′ = C5H3(SiMe3)2], with potassium graphite in THF in the presence of 2.2.2-cryptand generates [K(2.2.2-cryptand)][Cp′′3Th], 2, a complex containing thorium in the formal +2 oxidation state. Reaction of 1 with KC8in the presence of 18-crown-6 generates the analogous Th2+compound, [K(18-crown-6)(THF)2][Cp′′3Th], 3. Complexes 2 and 3 form dark green solutions in THF with ε = 23 000 M-1cm-1, but crystallize as dichroic dark blue/red crystals. X-ray crystallography revealed that the anions in 2 and 3 have trigonal planar coordination geometries, with 2.521 and 2.525 Å Th-(Cp′′ ring centroid) distances, respectively, equivalent to the 2.520 Å distance measured in 1. Density functional theory analysis of (Cp′′3Th)1-is consistent with a 6d2ground state, the first example of this transition metal electron configuration. Complex 3 reacts as a two-electron reductant with cyclooctatetraene to make Cp′′2Th(C8H8), 4, and [K(18-crown-6)]Cp′′. This journal is

Many UC-authored scholarly publications are freely available on this site because of the UC Academic Senate's Open Access Policy. Let us know how this access is important for you.

Main Content
Current View