Metal-Centered 17-Electron Radicals CpM(CO)3• (M = Cr, Mo, W): A Combined Negative Ion Photoelectron Spectroscopic and Theoretical Study
Despite the importance of group VI metal-centered 17-electron radicals CpM(CO)3 (Cp = 5-C5H5, 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 means of photodetachment photoelectron spectroscopy (PES) of their corresponding 18-electron anions and 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 to be 2.38 ± 0.02 (M = Cr), 2.63 ± 0.02 (Mo), and 2.63 ± 0.01 eV for (W), well correlated 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 largely from C5H5 moiety and contribute to the second spectral feature. The calculations further exhibit appreciable anion-to-neutral structural changes for all three species but with the change for the W species being the smallest, consistent with the W spectra being better resolved than the other two.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1074307
- Report Number(s):
- PNNL-SA-91192; 39732; 44678; KC0301020; KC0302010
- Journal Information:
- Organometallics, 32(7):2084-2091, Journal Name: Organometallics, 32(7):2084-2091
- Country of Publication:
- United States
- Language:
- English
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