{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,7]],"date-time":"2026-02-07T22:48:30Z","timestamp":1770504510635,"version":"3.49.0"},"reference-count":55,"publisher":"Wiley","issue":"12","license":[{"start":{"date-parts":[[2004,9,7]],"date-time":"2004-09-07T00:00:00Z","timestamp":1094515200000},"content-version":"vor","delay-in-days":3568,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["J Comput Chem"],"published-print":{"date-parts":[[1994,12]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Optimized equilibrium geometries and rotational transition structures for CH<jats:sub>3<\/jats:sub>OCH <jats:italic>X<\/jats:italic>CH<jats:sub>2<\/jats:sub> (<jats:italic>X<\/jats:italic> = H, F, CH<jats:sub>3<\/jats:sub>, NH<jats:sub>2<\/jats:sub>) and CH<jats:sub>3<\/jats:sub>OCF<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub> radicals are obtained by using unrestructed Hartree\u2010Fock (UHF) and second\u2010order M\u00f8ller\u2010Plesset perturbation (UMP2) theory; a standard 6\u201031G* basis set is used for geometry optmizations; single\u2010point energies for all stable rotamers are obtained at the UMP4\/6\u201031 + G*\/\/UMP2\/6\u201031G* level. By analysis of rotamers, it is apparent that an anomeric effect exists for <jats:italic>X<\/jats:italic> = F and to a lesser extent for <jats:italic>X<\/jats:italic> = NH<jats:sub>2<\/jats:sub>. Several isodesmic reactions have been studied for the purpose of obtaining theoretical heats of formation and stabilization energies (SE) of these \u03b2 substituted radicals and their \u03b1 isomers; the examination of computed SE shows that in the case of CH<jats:sub>3<\/jats:sub>OCHFCH<jats:sub>2<\/jats:sub> and CH<jats:sub>3<\/jats:sub>OCF<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub> radicals, a significant extra stabilization induced by the anomeric effect occurs. The question of <jats:italic>n<\/jats:italic><jats:sub>O<\/jats:sub> \u2192 \u03c3<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/tex2gif-stack-1.gif\" xlink:title=\"urn:x-wiley:01928651:media:JCC540151204:tex2gif-stack-1\"\/> negative hyperconjugation in \u03b2\u2010substituted radicals was explored with the aid of natural bond orbital (NBO) energetic analysis; it appears that <jats:italic>n<\/jats:italic><jats:sub>O<\/jats:sub> \u2192 \u03c3<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/tex2gif-stack-2.gif\" xlink:title=\"urn:x-wiley:01928651:media:JCC540151204:tex2gif-stack-2\"\/> delocalization plays a predominant role in the conformational preference and stabilization of \u03b2 fluoro derivatives; on the other hand, the stabilization arising from the oxygen lone pair into the \u03c3<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/tex2gif-stack-3.gif\" xlink:title=\"urn:x-wiley:01928651:media:JCC540151204:tex2gif-stack-3\"\/> orbital does not appear to be the key factor in the conformational preference of the CH<jats:sub>3<\/jats:sub>OCHNH<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub> radical. \u00a9 1994 by John Wiley &amp; Sons, Inc.<\/jats:p>","DOI":"10.1002\/jcc.540151204","type":"journal-article","created":{"date-parts":[[2005,1,2]],"date-time":"2005-01-02T01:00:45Z","timestamp":1104627645000},"page":"1341-1356","source":"Crossref","is-referenced-by-count":10,"title":["<i>Ab initio<\/i> study of some CH<sub>3<\/sub>OC<i>X<\/i>YCH<sub>2<\/sub> radicals: The influence of anomeric effects on their structure and their stability"],"prefix":"10.1002","volume":"15","author":[{"given":"R.","family":"Arnaud","sequence":"first","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2004,9,7]]},"reference":[{"key":"e_1_2_1_2_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-1-4613-3427-9_6"},{"key":"e_1_2_1_2_3","doi-asserted-by":"publisher","DOI":"10.1021\/cr00006a006"},{"key":"e_1_2_1_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198204011"},{"key":"e_1_2_1_3_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198307531"},{"key":"e_1_2_1_3_4","doi-asserted-by":"publisher","DOI":"10.1002\/kin.550250405"},{"key":"e_1_2_1_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00076a097"},{"key":"e_1_2_1_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00160a023"},{"key":"e_1_2_1_5_3","first-page":"471","volume":"16","author":"Arnaud R.","year":"1992","journal-title":"New J. 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