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Electron spin resonance spectra of the phosphoranyl radicals ROPF_3

Colussi, A. J. and Morton, J. R. and Preston, K. F. (1975) Electron spin resonance spectra of the phosphoranyl radicals ROPF_3. Journal of Physical Chemistry, 79 (6). pp. 651-654. ISSN 0022-3654 . http://resolver.caltech.edu/CaltechAUTHORS:20150623-154818015

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Abstract

Esr spectra recorded during the liquid-phase photolysis of solutions of PF_3 and F_2O or certain peroxides ROOR are attributed to the phosphoranyl radicals PF_4 and ROPF_3. The magnitudes of the observed ^(31)P and ^(19)F hyperfine interactions in these radicals are indicative of a totally symmetric half-filled molecular orbital in a trigonal bipyramidal framework. With the exception of the tert-butoxy group, the oxyl groups in ROPF_3 invariably occupy an apical position. Variations in the hyperfine interactions of the latter radicals with changes in RO are essentially restricted to those of the ^(31)P nucleus and the apical ^(19)F nucleus, an effect reminiscent of the trans influence of ligands in metal complexes. INDO MO calculations reproduce qualitatively some of the experimental observations.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/j100573a020DOIArticle
http://pubs.acs.org/doi/abs/10.1021/j100573a020PublisherArticle
ORCID:
AuthorORCID
Colussi, A. J.0000-0002-3400-4101
Alternate Title:Electron spin resonance spectra of the phosphoranyl radicals ROPF3
Additional Information:© 1975 American Chemical Society. (Received August 26, 1974)
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Funding AgencyGrant Number
National Research Council of CanadaUNSPECIFIED
Record Number:CaltechAUTHORS:20150623-154818015
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150623-154818015
Official Citation:Electron spin resonance spectra of the phosphoranyl radicals ROPF3 A. J. Colussi, J. R. Morton, and K. F. Preston The Journal of Physical Chemistry 1975 79 (6), 651-654 DOI: 10.1021/j100573a020
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58559
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:24 Jun 2015 14:44
Last Modified:13 Feb 2019 18:06

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