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Structurally Flexible Oxocarbenium/Borohydride Ion Pair: Dynamics of Hydride Transfer on the Background of Conformational Roaming
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0003-1028-3035
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Number of Authors: 22018 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 122, no 23, p. 5098-5106Article in journal (Refereed) Published
Abstract [en]

We apply Born-Oppenheimer molecular dynamics to the practically significant [dioxane-H(+)-acetone]-[(C6F5)(3)B-H(-)] and [Et2O-H(+)-OCPr2][(C6F5)(3)B-H(-)] ion pair intermediates. Dynamics of hydride transfer in cation/anion ion pair takes place on the background of large amplitude configurational changes. Geometry of oxocarbenium/borohydride ion pairs is flexible, meaning that we uncover significant actual structural disorder at a finite temperature. Therefore, although the starting structure can be fairly close to the configurational area of the hydride transfer transition state (TS) and despite a low potential energy barrier (ca. 1.5 kcal/mol, according to the literature), already at T approximate to 325 K the system can remain ignorant of the TS region and move round and about (roam) in the configurational space for a period of time in the range between 10 and 100 ps. This indicates structural flexibility of oxocarbenium/borohydride ion pair on apparently a flat potential energy landscape of cation/anion interaction, and this has not been taken into consideration by the free energy estimations in static considerations made thus far. The difference between the dynamics-based representation of the system versus the static representation amounts to the difference between quasi-bimolecular versus unimolecular descriptions of the hydride transfer step.

Place, publisher, year, edition, pages
2018. Vol. 122, no 23, p. 5098-5106
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-158187DOI: 10.1021/acs.jpca.8b02151ISI: 000435613800004PubMedID: 29812938OAI: oai:DiVA.org:su-158187DiVA, id: diva2:1234230
Available from: 2018-07-23 Created: 2018-07-23 Last updated: 2018-07-23Bibliographically approved

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