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

Lyon, Jonathan T. ; Andrews, Lester ; Malmqvist, Per-Åke LU ; Roos, Björn LU ; Yang, Tianxiao and Bursten, Bruce E. (2007) In Inorganic Chemistry 46(12). p.4917-4925
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... (More)
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. (Less)
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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Inorganic Chemistry
volume
46
issue
12
pages
4917 - 4925
publisher
The American Chemical Society (ACS)
external identifiers
  • wos:000246907800026
  • scopus:34347245989
  • pmid:17487964
ISSN
1520-510X
DOI
10.1021/ic062407w
language
English
LU publication?
yes
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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)
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a5a0e8f6-7f7c-4bc8-a5d2-6153e8b48616 (old id 651051)
date added to LUP
2016-04-01 11:43:23
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2020-12-16 01:19:06
@article{a5a0e8f6-7f7c-4bc8-a5d2-6153e8b48616,
  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.},
  author       = {Lyon, Jonathan T. and Andrews, Lester and Malmqvist, Per-Åke and Roos, Björn and Yang, Tianxiao and Bursten, Bruce E.},
  issn         = {1520-510X},
  language     = {eng},
  number       = {12},
  pages        = {4917--4925},
  publisher    = {The American Chemical Society (ACS)},
  series       = {Inorganic Chemistry},
  title        = {Infrared spectrum and bonding in uranium methylidene dihydride, CH2=UH2},
  url          = {http://dx.doi.org/10.1021/ic062407w},
  doi          = {10.1021/ic062407w},
  volume       = {46},
  year         = {2007},
}