Identification of the +2 oxidation state for uranium in a crystalline molecular complex, [K(2.2.2-Cryptand)][(C5H4SiMe 3)3U]

Matthew R. MacDonald, Megan E. Fieser, Jefferson E. Bates, Joseph W. Ziller, Filipp Furche, William J. Evans

Research output: Contribution to journalArticlepeer-review

137 Scopus citations

Abstract

Flash reduction of Cp′3U (Cp′ = C5H 4SiMe3) in a column of potassium graphite in the presence of 2.2.2-cryptand generates crystalline [K(2.2.2-cryptand)] [Cp′3U], the first isolable molecular U2+ complex. To ensure that this was not the U3+ hydride, [K(2.2.2-cryptand)] [Cp′3UH], which could be crystallographically similar, the hydride complex was synthesized by addition of KH to Cp′3U and by reduction of H2 by the U2+ complex and was confirmed to be a different compound. Density functional theory calculations indicate a 5f36d1 quintet ground state for the [Cp′ 3U]- anion and match the observed strong transitions in its optical spectrum.

Original languageEnglish (US)
Pages (from-to)13310-13313
Number of pages4
JournalJournal of the American Chemical Society
Volume135
Issue number36
DOIs
StatePublished - Sep 11 2013

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