{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T19:28:28Z","timestamp":1760297308979},"reference-count":41,"publisher":"Wiley","issue":"8","license":[{"start":{"date-parts":[[2004,9,7]],"date-time":"2004-09-07T00:00:00Z","timestamp":1094515200000},"content-version":"vor","delay-in-days":3325,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["J Comput Chem"],"published-print":{"date-parts":[[1995,8]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p><jats:italic>Ab initio<\/jats:italic> molecular orbital (<jats:italic>MO<\/jats:italic>) calculations are carried out on the nonidentity allyl transfer processes, X<jats:sup>\u2212<\/jats:sup> + CH<jats:sub>2<\/jats:sub>CHCH<jats:sub>2<\/jats:sub>Y \u21cc CH<jats:sub>2<\/jats:sub>CHCH<jats:sub>2<\/jats:sub> X + Y<jats:sup>\u2212<\/jats:sup>, with X<jats:sup>\u2212<\/jats:sup> = H, F, and Cl and Y = H, NH<jats:sub>2<\/jats:sub>, OH, F, PH<jats:sub>2<\/jats:sub>, SH, and Cl. The Marcus equation applies well to the allyl transfer reactions. The transition state (TS) position along the reaction coordinate and the TS structure are strongly influenced by the thermodynamic driving force, whereas the TS looseness is originated from the intrinsic barrier. The intrinsic barrier, \u0394<jats:italic>E<\/jats:italic><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:JCC540160811:tex2gif-stack-1\" \/>, looseness, %<jats:italic>L<\/jats:italic>\u2021, and absolute asymmetry, %<jats:italic>AS<\/jats:italic>\u2021, are well correlated with the percentage bond elongation, %<jats:italic>CY<\/jats:italic>\u2021 = [(<jats:italic>d<\/jats:italic><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:JCC540160811:tex2gif-stack-2\" \/> \u2212 <jats:italic>d<\/jats:italic><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:JCC540160811:tex2gif-stack-3\" \/>)\/<jats:italic>d<\/jats:italic><jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/tex2gif-stack-4.gif\" xlink:title=\"urn:x-wiley:01928651:media:JCC540160811:tex2gif-stack-4\" \/>] \u00d7 100 and\/or %<jats:italic>CX<\/jats:italic>\u2021. The %<jats:italic>CY<\/jats:italic>\u2021 and the bond orders indicate that a stronger nucleophile and\/or a stronger nucleofuge (or a better leaving group) leads to an earlier TS on the reaction coordinate with a lesser degree of bond making as well as bond breaking. These are consistent with the Bell\u2010Evans\u2010Polanyi principle and the Leffler\u2010Hammond postulate. \u00a9 1995 by John Wiley &amp; Sons, Inc.<\/jats:p>","DOI":"10.1002\/jcc.540160811","type":"journal-article","created":{"date-parts":[[2005,1,2]],"date-time":"2005-01-02T08:40:29Z","timestamp":1104655229000},"page":"1045-1054","source":"Crossref","is-referenced-by-count":25,"title":["<i>Ab initio<\/i> molecular orbital studies of nonidentity allyl transfer reactions"],"prefix":"10.1002","volume":"16","author":[{"given":"Ikchoon","family":"Lee","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Chang Kon","family":"Kim","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Bon\u2010Su","family":"Lee","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2004,9,7]]},"reference":[{"key":"e_1_2_1_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00095a025"},{"key":"e_1_2_1_2_3","unstructured":"For identity allyl transfer reactions seeJ. 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