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Infrared multiphoton dissociation spectrum of CF_3Mn(CO)_3(NO)^-

Shin, Seung Koo and Beauchamp, J. L. (1990) Infrared multiphoton dissociation spectrum of CF_3Mn(CO)_3(NO)^-. Journal of the American Chemical Society, 112 (6). pp. 2066-2069. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20180430-145300967

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Abstract

An infrared multiphoton dissociation spectrum of CF_3Mn(CO)(NO)^- has been obtained with Fourier transform ion cyclotron resonance spectroscopy combined with a line-tunable continuous wave CO_2 laser in the 925-1085 cm^(-1) wavelength range. The trifluoromethyl group in the anion shows two absorption maxima at 1045 and 980 cm^(-1). The peak at 1045 is assigned as a C-F stretch of A_1-type symmetry and the peak at 980 cm^(-1) is ascribed to a C-F stretch of E-type symmetry. It is quite interesting to observe that the symmetric C-F stretching mode changes little in frequency from 1063 cm^(-1) for CF_3Mn(CO)_5 to 1045 cm^(-1) for CF_3Mn(CO)_3(NO)^-, while the C-F stretching frequency of E-type symmetry decreases from 1043 cm^(-1) for the 18 e^- neutral precursor to 980 cm^(-1) for the 18 e^- anion. Comparison with the infrared multiphoton dissociation spectrum of CF_3Mn(CO)_4^- ion reveals that the degenerate C-F stretch of E-type symmetry increases from 945 cm^(-1) for the 17 e^- CF_3Mn(CO)_4^- to 980 cm^-1) for the 18 e^- CF_3Mn(CO)_3(NO)^-, whereas the symmetric C-F stretching bands overlap with each other within experimental uncertainties. Variations of the electron density and hybridization in the σ donor orbital of the CF_3 ligand due to the different d orbital splittings of the complexes may be responsible for the distinctive C-F stretching frequencies observed in CF_3Mn(CO)_5 (18 e^-), CF_3Mn(CO)_4^- (17 e^-), and CF_3Mn(CO)_3(NO)^- (18 e^-).


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/ja00162a004DOIArticle
ORCID:
AuthorORCID
Beauchamp, J. L.0000-0001-8839-4822
Alternate Title:Infrared multiphoton dissociation spectrum of CF3Mn(CO)3(NO)-
Additional Information:© 1990 American Chemical Society. Received August 9, 1989. We acknowledge the support of the National Science Foundation (Grant No. CHE87-11567) and the donors of the Petroleum Research Fund, administered by the American Chemical Society.
Funders:
Funding AgencyGrant Number
NSFCHE87-11567
American Chemical Society Petroleum Research FundUNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Arthur Amos Noyes Laboratory of Chemical Physics7952
Issue or Number:6
Record Number:CaltechAUTHORS:20180430-145300967
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180430-145300967
Official Citation:Infrared multiphoton dissociation spectrum of CF3Mn(CO)3(NO)- Seung Koo Shin and J. L. Beauchamp Journal of the American Chemical Society 1990 112 (6), 2066-2069 DOI: 10.1021/ja00162a004
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86134
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:01 May 2018 14:39
Last Modified:03 Oct 2019 19:39

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