Infrared spectrum and bonding in uranium methylidene dihydride, CH2=UH2

Jonathan T. Lyon, Lester Andrews, Per-Åke Malmqvist, Björn Roos, Tianxiao Yang, Bruce E. Bursten

Research output: Contribution to journalArticlepeer-review

58 Citations (SciVal)

Abstract

Uranium atoms activate methane upon ultraviolet excitation to form the methyl uranium hydride CH3-UH, which undergoes alpha-H transfer to produce uranium methylidene dihydride, CH2UH2. This rearrangement most likely occurs on an excited-quintet potential-energy surface and is followed by relaxation in the argon matrix. These simple U + CH4 reaction products are identified through isotopic substitution ((CH4)-C-13, CD4, CH2D2) and density functional theory frequency and structure calculations for the strong U-H stretching modes. Relativistic multiconfiguration (CASSCF/CASPT2) calculations substantiate the agostic distorted C-1 ground-state structure for the triplet CH2UH2 molecule. We find that uranium atoms are less reactive in methane activation than thorium atoms. Our calculations show that the CH2UH2 complex is distorted more than CH2ThH2. A favorable interaction between the low energy open-shell U(5f) sigma orbital and the agostic hydrogen contributes to the distortion in the uranium methylidene complexes.
Original languageEnglish
Pages (from-to)4917-4925
JournalInorganic Chemistry
Volume46
Issue number12
DOIs
Publication statusPublished - 2007

Bibliographical note

The information about affiliations in this record was updated in December 2015.
The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)

Subject classification (UKÄ)

  • Theoretical Chemistry

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