Identification of the +2 Oxidation State for Uranium in a Crystalline Molecular Complex, [K(2.2.2-Cryptand)][(CHSiMe)U].

Flash reduction of Cp′U (Cp′ = CHSiMe) in a column of potassium graphite in the presence of 2.2.2-cryptand generates crystalline [K(2.2.2-cryptand)][Cp′U], the first isolable molecular U complex. To ensure that this was not the U hydride, [K(2.2.2-cryptand)][Cp′UH], which could be crystallographical...

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Detalles Bibliográficos
Publicado en:	Journal of the American Chemical Society Vol. 135; no. 36; pp. 13310 - 13314
Autores principales:	MacDonald, Matthew R., Fieser, Megan E., Bates, Jefferson E., Ziller, Joseph W., Furche, Filipp, Evans, William J.
Formato:	Artículo
Publicado:	American Chemical Society 9/11/2013
Materias:	Uranium compounds synthesis Oxidation states Density functional theory Hydrides Cryptands Potassium compounds Graphite X-ray crystallography
Acceso en línea:	Ver este registro en EBSCOhost

Descripción
Sumario:	Flash reduction of Cp′U (Cp′ = CHSiMe) in a column of potassium graphite in the presence of 2.2.2-cryptand generates crystalline [K(2.2.2-cryptand)][Cp′U], the first isolable molecular U complex. To ensure that this was not the U hydride, [K(2.2.2-cryptand)][Cp′UH], which could be crystallographically similar, the hydride complex was synthesized by addition of KH to Cp′U and by reduction of H by the U complex and was confirmed to be a different compound. Density functional theory calculations indicate a 5f³6d¹ quintet ground state for the [Cp′U] anion and match the observed strong transitions in its optical spectrum.