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. doi:10.1021/ja00162a004. 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^-).
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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. | ||||||
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Issue or Number: | 6 | ||||||
DOI: | 10.1021/ja00162a004 | ||||||
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: | 15 Nov 2021 20:35 |
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