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Ed."},{"key":"ref12\/cit12","unstructured":"We note that both rate constants reflect the saturation coverage of either butoxides in 1-butene double bond isomerization or adsorbed butanol monomers in 2-butanol dehydration and allow rigorous conclusions with respect to the kinetic relevance of the butoxide desorption and the elimination step."},{"key":"ref13\/cit13","unstructured":"The high pre-exponential factor of the elimination step leads to rate constants for the elimination and butene desorption steps that differ less than expected from the calculated barriers (see also section 3.2)."},{"key":"ref14\/cit14","unstructured":"The rotational barriers for the interconversion of the different stereoisomers are low (\u223c10 to 15 kJ mol\n                      \u22121\n                      )Anslyn, E. V. and Dougherty, D. A.Modern Physical Organic Chemistry;University Science Books: New York, 2006; p93."},{"key":"ref15\/cit15","unstructured":"The difference in \u2009\u03bdO-H and \u03bdO-D stretching vibrations is estimated to be about 700 cm\n                      \u22121\n                      for 2-propanol-\n                      d\n                      0\n                      and 2-propanol-\n                      d\n                      8\n                      H-bonded to H\n                      2\n                      SO\n                      4\n                      by DFT, corresponding to zero point energy differences \u0394ZPE(D) \u2212 ZPE(H) of about 8.3 kJ\/mol, leading to a KIE of 18.8."},{"key":"ref16\/cit16","doi-asserted-by":"crossref","first-page":"252","DOI":"10.1016\/0021-9517(70)90098-9","volume":"17","author":"Kn\u00f6zinger H.","year":"1970","journal-title":"J. Catal."},{"key":"ref17\/cit17","unstructured":"Anslyn, E. V. and Dougherty, D. A.Modern Physical Organic Chemistry;University Science Books: New York, 2006; p429."},{"key":"ref18\/cit18a","volume-title":"Hydrogen Transfer Reactions","author":"Hynes J. T.","year":"2007"},{"key":"ref18\/cit18b","doi-asserted-by":"crossref","first-page":"83","DOI":"10.1126\/science.1117756","volume":"310","author":"Mohammed O. F.","year":"2005","journal-title":"Science"},{"key":"ref18\/cit18c","first-page":"285","volume":"2","author":"Eigen M.","year":"1964","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref19\/cit19","unstructured":"Aue, D. H. and Bowers, M. T.Gas Phase Ion Chemistry;Academic Press: New York, 1970, Vol. 2, p32."},{"key":"ref20\/cit20","volume-title":"The Chemical Thermodynamics of Organic Compounds","author":"Stull D. R.","year":"1987"},{"key":"ref21\/cit21","doi-asserted-by":"crossref","first-page":"413","DOI":"10.1063\/1.556018","volume":"27","author":"Hunter E. P. L.","year":"1998","journal-title":"J. Phys. Chem. Ref. Data"},{"key":"ref22\/cit22","doi-asserted-by":"crossref","first-page":"434","DOI":"10.1016\/0021-9517(86)90331-3","volume":"98","author":"Aronson M. T.","year":"1986","journal-title":"J. Catal."},{"key":"ref23\/cit23","doi-asserted-by":"crossref","first-page":"1556","DOI":"10.1021\/ja9729037","volume":"120","author":"Br\u00e4ndle M.","year":"1998","journal-title":"J. Am. Chem. Soc."},{"key":"ref24\/cit24","doi-asserted-by":"crossref","first-page":"5114","DOI":"10.1021\/ja0000753","volume":"122","author":"Koppel I. A.","year":"2000","journal-title":"J. Am. Chem. Soc."},{"key":"ref25\/cit25","unstructured":"The \u0394\n                      E\n                      int\n                      term of the late transition state (H\n                      2\n                      O)R\n                      +\n                      \u00b7\u00b7\u00b7POM\n                      \u2212\n                      ) ion-pair also includes the stabilizing R\n                      +\n                      \u00b7\u00b7\u00b7H\n                      2\n                      O (ion-dipole) interaction."},{"key":"ref26\/cit26","doi-asserted-by":"crossref","first-page":"2904","DOI":"10.1002\/qua.21115","volume":"106","author":"Robbins A. D.","year":"2006","journal-title":"Int. J. Quantum Chem."},{"key":"ref27\/cit27","doi-asserted-by":"crossref","first-page":"134","DOI":"10.1016\/j.cattod.2005.04.014","volume":"105","author":"Janik M. J.","year":"2005","journal-title":"Catal. Today"},{"key":"ref28\/cit28","doi-asserted-by":"crossref","first-page":"4738","DOI":"10.1021\/la047395a","volume":"21","author":"Campbell K. A.","year":"2004","journal-title":"Langmuir"},{"key":"ref29\/cit29","volume-title":"Thermochemical Kinetics","author":"Benson S. W.","year":"1976"},{"key":"ref30\/cit30","doi-asserted-by":"crossref","first-page":"1257","DOI":"10.1021\/ja00317a015","volume":"106","author":"Meot-Ner (Mautner) M.","year":"1984","journal-title":"J. Am. Chem. Soc."},{"key":"ref31\/cit31","doi-asserted-by":"crossref","first-page":"3641","DOI":"10.1021\/cr0103569","volume":"102","author":"Okuhara T.","year":"2002","journal-title":"Chem. Rev."},{"key":"ref32\/cit32","unstructured":"Charge transfer from POM\n                      \u2212\n                      to the dimer (ROH)\n                      2\n                      H\n                      +\n                      is indicated by two O\n                      alkanol\n                      -H\n                      alkanol\n                      \u00b7\u00b7\u00b7O\n                      POM\n                      hydrogen bonds between the cationic dimer and the anionic conjugate base [ref 10]."}],"container-title":["Journal of the American Chemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/ja803114r","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,3,7]],"date-time":"2023-03-07T08:59:35Z","timestamp":1678179575000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/doi\/10.1021\/ja803114r"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2008,7,10]]},"references-count":34,"journal-issue":{"issue":"31","published-print":{"date-parts":[[2008,8,1]]}},"alternative-id":["10.1021\/ja803114r"],"URL":"https:\/\/doi.org\/10.1021\/ja803114r","relation":{},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2008,7,10]]}}}