Metal-centered 17-electron radicals CpM(CO)3• (M = Cr, Mo, W): A combined negative ion photoelectron spectroscopic and theoretical study

Edwin F. Van Der Eide, Gao Lei Hou, S. H M Deng, Hui Wen, Ping Yang, R Morris Bullock, Xue Bin Wang

Research output: Contribution to journalArticle

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Abstract

Despite the importance of group 6 metal-centered 17-electron radicals CpM(CO)3 (M = Cr, Mo, W) in establishing many of the fundamental reactions now known for metal-centered radicals, spectroscopic characterization of their electronic properties and structures has been very challenging, due to their high reactivity. Here we report a gas-phase study of these species by photodetachment photoelectron spectroscopy (PES) of their corresponding 18-electron anions and by theoretical electronic structure calculations. Three well-separated spectral features are observed by PES for each anionic species. Electron affinities (EAs) of CpM(CO)3 were experimentally measured from the threshold of each spectrum and were found to be 2.38 ± 0.02 (M = Cr), 2.63 ± 0.02 (Mo), and 2.63 ± 0.01 eV (W). These experimental values correlate well with the reported redox potentials measured in solution. Theoretical calculations for all anionic and neutral (radical) species gave calculated EAs and band gaps that are in good agreement with the experimental data. Molecular orbital (MO) analyses for each anion indicate that the top three occupied MOs are mainly metal-based and contribute to the first spectral feature, whereas the next two MOs are associated with Cp-M π bonding and contribute to the second spectral feature. The calculations further exhibit appreciable anion-to-neutral structural changes for all three species, with the change for the W species being the smallest.

Original languageEnglish
Pages (from-to)2084-2091
Number of pages8
JournalOrganometallics
Volume32
Issue number7
DOIs
Publication statusPublished - Apr 8 2013

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Carbon Monoxide
Photoelectrons
negative ions
Anions
Electron affinity
photoelectrons
Negative ions
Metals
Photoelectron spectroscopy
anions
electron affinity
Electronic structure
Electrons
photoelectron spectroscopy
metals
electrons
photodetachment
Molecular orbitals
Electronic properties
molecular orbitals

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Metal-centered 17-electron radicals CpM(CO)3• (M = Cr, Mo, W) : A combined negative ion photoelectron spectroscopic and theoretical study. / Van Der Eide, Edwin F.; Hou, Gao Lei; Deng, S. H M; Wen, Hui; Yang, Ping; Bullock, R Morris; Wang, Xue Bin.

In: Organometallics, Vol. 32, No. 7, 08.04.2013, p. 2084-2091.

Research output: Contribution to journalArticle

Van Der Eide, Edwin F. ; Hou, Gao Lei ; Deng, S. H M ; Wen, Hui ; Yang, Ping ; Bullock, R Morris ; Wang, Xue Bin. / Metal-centered 17-electron radicals CpM(CO)3• (M = Cr, Mo, W) : A combined negative ion photoelectron spectroscopic and theoretical study. In: Organometallics. 2013 ; Vol. 32, No. 7. pp. 2084-2091.
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