Spectroscopic Characterization, Computational Investigation, and Comparisons of ECX
Name
ECX-revison May 9 2017 clean.pdf
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Author(s)
Hou, Gao-Lei
Chen, Bo
Transue, Wesley J.
Yang, Zheng
Grützmacher, Hansjörg
Driess, Matthias
Cummins, Christopher C.
Borden, Weston Thatcher
Wang, Xue-Bin
Date Issued
July 2017
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Hou, Gao-Lei et al. “Spectroscopic Characterization, Computational Investigation, and Comparisons of ECX– (E = As, P, and N; X = S and O) Anions.” Journal of the American Chemical Society 139, 26 (June 2017): 8922–8930 © 2017 American Chemical Society
Version
Author's final manuscript
Abstract
Three newly synthesized [Na+(221-Kryptofix)] salts containing AsCO–, PCO–, and PCS– anions were successfully electrosprayed into a vacuum, and these three ECX– anions were investigated by negative ion photoelectron spectroscopy (NIPES) along with high-resolution photoelectron imaging spectroscopy. For each ECX– anion, a well-resolved NIPE spectrum was obtained, in which every major peak is split into a doublet. The splittings are attributed to spin–orbit coupling (SOC) in the ECX• radicals. Vibrational progressions in the NIPE spectra of ECX– were assigned to the symmetric and the antisymmetric stretching modes in ECX• radicals. The electron affinities (EAs) and SO splittings of ECX• are determined from the NIPE spectra to be AsCO•: EA = 2.414 ± 0.002 eV, SO splitting = 988 cm–1; PCO•: EA = 2.670 ± 0.005 eV, SO splitting = 175 cm–1; PCS•: EA = 2.850 ± 0.005 eV, SO splitting = 300 cm–1. Calculations using the B3LYP, CASPT2, and CCSD(T) methods all predict linear geometries for both the anions and the neutral radicals. The calculated EAs and SO splittings for ECX• are in excellent agreement with the experimentally measured values. The simulated NIPE spectra, which are based on the calculated Franck–Condon factors, and the SO splittings nicely reproduce all of the observed spectral peaks, thus allowing unambiguous spectral assignments. The finding that PCS• has the greatest EA of the three triatomic molecules considered here is counterintuitive based upon simple electronegativity considerations, but this finding is understandable in terms of the movement of electron density from phosphorus in the HOMO of PCO– to sulfur in the HOMO of PCS–. Comparisons of the EAs of PCO• and PCS• with the previously measured EA values for NCO• and NCS• are made and discussed.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/jacs.7b02984
