{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,8]],"date-time":"2026-09-08T09:07:22Z","timestamp":1788858442653,"version":"build-2803163510"},"reference-count":46,"publisher":"American Chemical Society (ACS)","issue":"5","license":[{"start":{"date-parts":[[2015,2,5]],"date-time":"2015-02-05T00:00:00Z","timestamp":1423094400000},"content-version":"vor","delay-in-days":365,"URL":"https:\/\/pubs.acs.org\/page\/policy\/authorchoice_termsofuse.html"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2014,3,7]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>We recently reported abnormal secondary deuterium kinetic isotope effects (2\u00b0 KIEs) for hydride transfer reactions from alcohols to carbocations in acetonitrile (Chem. Comm. 2012, 48, 11337). Experimental 2\u00b0 KIE values were found to be inflated on the 9-C position in the xanthylium cation but deflated on the \u03b2-C position in 2-propanol with respect to the values predicted by the semi-classical transition-state theory. No primary (1\u00b0) isotope effect on 2\u00b0 KIEs was observed. Herein, the KIEs were replicated by the Marcus-like H-tunneling model that requires a longer donor\u2013acceptor distance (DAD) in a lighter isotope transfer process. The 2\u00b0 KIEs for a range of potential tunneling-ready-states (TRSs) of different DADs were calculated and fitted to the experiments to find the TRS structure. The observed no effect of 1\u00b0 isotope on 2\u00b0 KIEs is explained in terms of the less sterically hindered TRS structure so that the change in DAD due to the change in 1\u00b0 isotope does not significantly affect the reorganization of the 2\u00b0 isotope and hence the 2\u00b0 KIE. The effect of 1\u00b0 isotope on 2\u00b0 KIEs may be expected to be more pronounced and thus observable in reactions occurring in restrictive environments such as the crowded and relatively rigid active site of enzymes.<\/jats:p>","DOI":"10.1021\/jo402650a","type":"journal-article","created":{"date-parts":[[2014,2,5]],"date-time":"2014-02-05T11:06:26Z","timestamp":1391598386000},"page":"1989-1994","source":"Crossref","is-referenced-by-count":13,"title":["Computational Replication\nof the Abnormal Secondary\nKinetic Isotope Effects in a Hydride Transfer Reaction in Solution\nwith a Motion Assisted H-Tunneling Model"],"prefix":"10.1021","volume":"79","author":[{"given":"Sadra","family":"Kashefolgheta","sequence":"first","affiliation":[{"name":"Southern Illinois University Edwardsville , , , ,","place":["Edwardsville, Illinois, United States, 62026"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mortezaali","family":"Razzaghi","sequence":"additional","affiliation":[{"name":"Southern Illinois University Edwardsville , , , ,","place":["Edwardsville, Illinois, United States, 62026"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Blake","family":"Hammann","sequence":"additional","affiliation":[{"name":"Southern Illinois University Edwardsville , , , ,","place":["Edwardsville, Illinois, United States, 62026"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"James","family":"Eilers","sequence":"additional","affiliation":[{"name":"Southern Illinois University Edwardsville , , , ,","place":["Edwardsville, Illinois, United States, 62026"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Daniel","family":"Roston","sequence":"additional","affiliation":[{"name":"The University of Iowa , , , ,","place":["Iowa City, Iowa, United States, 52242"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yun","family":"Lu","sequence":"additional","affiliation":[{"name":"Southern Illinois University Edwardsville , , , ,","place":["Edwardsville, Illinois, United States, 62026"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2014,2,5]]},"reference":[{"key":"2026090314041078700_cit1","doi-asserted-by":"crossref","first-page":"559","DOI":"10.1002\/poc.1746","volume":"23","author":"More O\u2019Ferrall","year":"2010","journal-title":"J. Phy. Org. Chem."},{"key":"2026090314041078700_cit2","doi-asserted-by":"crossref","DOI":"10.1007\/978-1-4899-2891-7","volume-title":"The Tunnel Effect\nin Chemistry","author":"Bell","year":"1980"},{"key":"2026090314041078700_cit3","doi-asserted-by":"crossref","first-page":"496","DOI":"10.1038\/20981","volume":"399","author":"Kohen","year":"1999","journal-title":"Nature"},{"key":"2026090314041078700_cit4","doi-asserted-by":"crossref","first-page":"3218","DOI":"10.1021\/bi982719d","volume":"38","author":"Basran","year":"1999","journal-title":"Biochemistry"},{"key":"2026090314041078700_cit5","doi-asserted-by":"crossref","first-page":"1189","DOI":"10.1021\/bi991941v","volume":"39","author":"Harris","year":"2000","journal-title":"Biochemistry"},{"key":"2026090314041078700_cit6","doi-asserted-by":"crossref","first-page":"8194","DOI":"10.1021\/ja025758s","volume":"124","author":"Francisco","year":"2002","journal-title":"J. Am. Chem. Soc."},{"key":"2026090314041078700_cit7","doi-asserted-by":"crossref","first-page":"4778","DOI":"10.1021\/ja031683w","volume":"126","author":"Sikorski","year":"2004","journal-title":"J. Am. Chem. Soc."},{"key":"2026090314041078700_cit8","doi-asserted-by":"crossref","first-page":"1307","DOI":"10.1098\/rstb.2006.1871","volume":"361","author":"Wang","year":"2006","journal-title":"Philos. Trans. R. Soc., B"},{"key":"2026090314041078700_cit9","doi-asserted-by":"crossref","first-page":"9820","DOI":"10.1021\/ja103010b","volume":"132","author":"Wang","year":"2010","journal-title":"J.\nAm. Chem. Soc."},{"key":"2026090314041078700_cit10","doi-asserted-by":"crossref","first-page":"1738","DOI":"10.1021\/ja209425w","volume":"134","author":"Stojkovic\u0327","year":"2012","journal-title":"J. Am. Chem. Soc."},{"key":"2026090314041078700_cit11","doi-asserted-by":"crossref","first-page":"869","DOI":"10.1021\/ja00316a007","volume":"106","author":"Gerritzen","year":"1984","journal-title":"J. Am. Chem. Soc."},{"key":"2026090314041078700_cit12","doi-asserted-by":"crossref","first-page":"5900","DOI":"10.1021\/ja010271p","volume":"123","author":"Lu","year":"2001","journal-title":"J. Am. Chem. Soc."},{"key":"2026090314041078700_cit13","doi-asserted-by":"crossref","first-page":"1579","DOI":"10.1021\/ja003607o","volume":"123","author":"Zhao","year":"2001","journal-title":"J. Am. Chem. Soc."},{"key":"2026090314041078700_cit14","doi-asserted-by":"crossref","first-page":"10877","DOI":"10.1021\/ja030120h","volume":"125","author":"Doll","year":"2003","journal-title":"J. Am. Chem. Soc."},{"key":"2026090314041078700_cit15","doi-asserted-by":"crossref","first-page":"164","DOI":"10.1021\/ja00287a029","volume":"107","author":"Saunders","year":"1985","journal-title":"J. Am. Chem. Soc."},{"key":"2026090314041078700_cit16","doi-asserted-by":"crossref","first-page":"6107","DOI":"10.1021\/ja00093a007","volume":"116","author":"Lin","year":"1994","journal-title":"J. Am. Chem. Soc."},{"key":"2026090314041078700_cit17","first-page":"743","volume-title":"Isotope Effects in\nChemistry and Biology","author":"Kohen","year":"2006"},{"key":"2026090314041078700_cit18","doi-asserted-by":"crossref","first-page":"361","DOI":"10.1002\/poc.610040607","volume":"4","author":"Huskey","year":"1991","journal-title":"J. Phys. Org.\nChem."},{"key":"2026090314041078700_cit19","doi-asserted-by":"crossref","first-page":"132","DOI":"10.1039\/9781847559975-00132","volume-title":"Quantum Tunnelling\nin Enzyme-Catalyzed Reactions","author":"Klinman","year":"2009"},{"key":"2026090314041078700_cit20","doi-asserted-by":"crossref","first-page":"1325","DOI":"10.1126\/science.2646716","volume":"243","author":"Cha","year":"1989","journal-title":"Science"},{"key":"2026090314041078700_cit21","doi-asserted-by":"crossref","first-page":"3543","DOI":"10.1021\/bi00556a020","volume":"19","author":"Blanchard","year":"1980","journal-title":"Biochemistry"},{"key":"2026090314041078700_cit22","doi-asserted-by":"crossref","first-page":"5479","DOI":"10.1021\/bi00318a016","volume":"23","author":"Hermes","year":"1984","journal-title":"Biochemistry"},{"key":"2026090314041078700_cit23","doi-asserted-by":"crossref","first-page":"1817","DOI":"10.1021\/bi00510a016","volume":"20","author":"Cook","year":"1981","journal-title":"Biochemistry"},{"key":"2026090314041078700_cit24","doi-asserted-by":"crossref","first-page":"5704","DOI":"10.1021\/ja00355a038","volume":"105","author":"Huskey","year":"1983","journal-title":"J. Am. Chem. Soc."},{"key":"2026090314041078700_cit25","doi-asserted-by":"crossref","first-page":"6577","DOI":"10.1021\/ja0732330","volume":"130","author":"Wilde","year":"2008","journal-title":"J. Am. Chem. Soc."},{"key":"2026090314041078700_cit26","doi-asserted-by":"crossref","first-page":"5894","DOI":"10.1021\/bi00238a013","volume":"30","author":"Bahnson","year":"1991","journal-title":"Biochemistry"},{"key":"2026090314041078700_cit27","doi-asserted-by":"crossref","first-page":"5503","DOI":"10.1021\/bi00072a003","volume":"32","author":"Bahnson","year":"1993","journal-title":"Biochemistry"},{"key":"2026090314041078700_cit28","doi-asserted-by":"crossref","first-page":"6825","DOI":"10.1021\/jo300879r","volume":"77","author":"Liu","year":"2012","journal-title":"J.\nOrg. Chem."},{"key":"2026090314041078700_cit29","doi-asserted-by":"crossref","first-page":"11337","DOI":"10.1039\/c2cc36110h","volume":"48","author":"Hammann","year":"2012","journal-title":"Chem\nComm"},{"key":"2026090314041078700_cit30","doi-asserted-by":"crossref","first-page":"4763","DOI":"10.1021\/jo800820u","volume":"73","author":"Lu","year":"2008","journal-title":"J. Org. Chem."},{"key":"2026090314041078700_cit31","doi-asserted-by":"crossref","first-page":"6503","DOI":"10.1021\/jo9007628","volume":"74","author":"Lu","year":"2009","journal-title":"J. Org. Chem."},{"key":"2026090314041078700_cit32","doi-asserted-by":"crossref","first-page":"1172","DOI":"10.1002\/poc.1842","volume":"24","author":"Lu","year":"2011","journal-title":"J. Phys. Org. Chem."},{"key":"2026090314041078700_cit33","doi-asserted-by":"crossref","first-page":"161","DOI":"10.1038\/nchem.1223","volume":"4","author":"Hay","year":"2012","journal-title":"Nat. Chem."},{"key":"2026090314041078700_cit34","doi-asserted-by":"crossref","first-page":"PR41","DOI":"10.1021\/cr1001035","volume":"110","author":"Nagel","year":"2010","journal-title":"Chem. Rev."},{"key":"2026090314041078700_cit35","doi-asserted-by":"crossref","first-page":"179","DOI":"10.1016\/j.cplett.2009.01.038","volume":"471","author":"Klinman","year":"2009","journal-title":"Chem. Phys. Lett."},{"key":"2026090314041078700_cit36","doi-asserted-by":"crossref","first-page":"1085","DOI":"10.1139\/v99-099","volume":"77","author":"Kuznetsov","year":"1999","journal-title":"Can. J. Chem."},{"key":"2026090314041078700_cit37","doi-asserted-by":"crossref","first-page":"6643","DOI":"10.1021\/jp071589s","volume":"111","author":"Marcus","year":"2007","journal-title":"J. Phys. Chem.\nB."},{"key":"2026090314041078700_cit38","doi-asserted-by":"crossref","first-page":"6860","DOI":"10.1021\/bi300613e","volume":"51","author":"Roston","year":"2012","journal-title":"Biochemistry"},{"key":"2026090314041078700_cit39","doi-asserted-by":"crossref","first-page":"13624","DOI":"10.1021\/ja405917m","volume":"135","author":"Roston","year":"2013","journal-title":"J.\nAm. Chem. Soc."},{"key":"2026090314041078700_cit40","doi-asserted-by":"crossref","first-page":"9572","DOI":"10.1073\/pnas.1000931107","volume":"107","author":"Roston","year":"2010","journal-title":"Proc.\nNatl. Acad. Sci. U.S.A."},{"key":"2026090314041078700_cit41","doi-asserted-by":"crossref","first-page":"8197","DOI":"10.1021\/ja001476l","volume":"122","author":"Alhambra","year":"2000","journal-title":"J. Am. Chem. Soc."},{"key":"2026090314041078700_cit42","doi-asserted-by":"crossref","first-page":"8884","DOI":"10.1021\/jp001635n","volume":"104","author":"Webb","year":"2000","journal-title":"J. Phys. Chem. B"},{"key":"2026090314041078700_cit43","unstructured":"Anisinov, V.; Paneth, P.\n          ISOEFF07; Technical University of Lodz: Lodz, 2007."},{"key":"2026090314041078700_cit44","doi-asserted-by":"crossref","first-page":"675","DOI":"10.1063\/1.1747368","volume":"17","author":"Bigeleisen","year":"1949","journal-title":"J. Chem. Phys."},{"key":"2026090314041078700_cit46","doi-asserted-by":"crossref","first-page":"471","DOI":"10.1146\/annurev-biochem-051710-133623","volume":"82","author":"Klinman","year":"2013","journal-title":"Annu.\nRev. Biochem."},{"key":"2026090314041078700_cit47","doi-asserted-by":"crossref","first-page":"2018","DOI":"10.1021\/bi00654a032","volume":"15","author":"Klinman","year":"1976","journal-title":"Biochemistry"}],"container-title":["The Journal of Organic Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jo402650a","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/joceah\/article-pdf\/79\/5\/1989\/19599685\/jo402650a.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/joceah\/article-pdf\/79\/5\/1989\/19599685\/jo402650a.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,8]],"date-time":"2026-09-08T08:12:55Z","timestamp":1788855175000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/joceah\/article\/79\/5\/1989\/1761395\/Computational-Replication-of-the-Abnormal"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2014,2,5]]},"references-count":46,"journal-issue":{"issue":"5","published-online":{"date-parts":[[2014,2,5]]},"published-print":{"date-parts":[[2014,3,7]]}},"URL":"https:\/\/doi.org\/10.1021\/jo402650a","relation":{},"ISSN":["0022-3263","1520-6904"],"issn-type":[{"value":"0022-3263","type":"print"},{"value":"1520-6904","type":"electronic"}],"subject":[],"published":{"date-parts":[[2014,2,5]]}}}