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

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Abstract

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 KC8 in 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−1 cm−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 6d2 ground 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′′.

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

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Article information


Submitted
02 Oct 2014
Accepted
15 Oct 2014
First published
03 Nov 2014

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2015,6, 517-521
Article type
Edge Article

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

R. R. Langeslay, M. E. Fieser, J. W. Ziller, F. Furche and W. J. Evans, Chem. Sci., 2015, 6, 517
DOI: 10.1039/C4SC03033H

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