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Issue 44, 2019
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In search of tris(trimethylsilylcyclopentadienyl) thorium

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Abstract

Reduction of Cp′3ThCl, Cp′3ThBr, and Cp′3ThI (Cp′ = C5H4SiMe3) with potassium graphite generates dark blue solutions with reactivity and spectroscopic properties consistent with the formation of Cp′3Th. The EPR and UV-visible spectra of the solutions are similar to those of crystallographically-characterized tris(cyclopentadienyl) Th(III) complexes: [C5H3(SiMe3)2]3Th, (C5Me4H)3Th, (C5tBu2H3)3Th, and (C5Me5)3Th. Density functional theory (DFT) analysis indicates that the UV-visible spectrum is consistent with Cp′3Th and not [Cp′3ThBr]1−. Although single crystals of Cp′3Th have not been isolated, the blue solution reacts with Me3SiCl, I2, and HC[triple bond, length as m-dash]CPh to afford products expected from Cp′3Th, namely, Cp′3ThCl, Cp′3ThI, and Cp′3Th(C[triple bond, length as m-dash]CPh), respectively. Reactions with MeI give mixtures of Cp′3ThI and Cp′3ThMe. Evidence for further reduction of the blue solutions to a Cp′-ligated Th(II) complex has not been observed. The crystal structures of Cp′3ThMe and (Cp′3Th)2(μ-O) were also determined as part of these studies.

Graphical abstract: In search of tris(trimethylsilylcyclopentadienyl) thorium

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Publication details

The article was received on 13 Sep 2019, accepted on 17 Oct 2019 and first published on 18 Oct 2019


Article type: Paper
DOI: 10.1039/C9DT03674A
Dalton Trans., 2019,48, 16633-16640

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    In search of tris(trimethylsilylcyclopentadienyl) thorium

    J. C. Wedal, S. Bekoe, J. W. Ziller, F. Furche and W. J. Evans, Dalton Trans., 2019, 48, 16633
    DOI: 10.1039/C9DT03674A

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