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Surprisingly Flexible Oxonium/Borohydride Ion Pair Configurations
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 15, p. 3713-3727Article in journal (Refereed) Published
Abstract [en]

We investigate the geometry of oxonium/borohydride ion pairs [ether-H(+) ether] [LA-H(-)] with dioxane, THF, and Et2O as ethers and B(C6F5)(3) as the Lewis acid (LA). The question is about possible location of the disolvated proton [ether -H(+) -ether], with respect to the hydride of the structurally complex [LA -H(-)] anion. Using Born Oppenheimer molecular dynamics and a comparison of the potential and free energies of the optimized configurations, we show that herein considered ion pairs are much more flexible geometrically than previously thought. Conformers with different locations of cations with respect to anions are governed by a flat energy -landscape. We found a novel configuration in which oxonium is below [LA-11((-))], with respect to the direction of borane -> hydride vector, and the proton -hydride distance is ca. 6 A. With calculations of the vibrational spectra of [ether-H(+)-ether][(C6F5)(3)B-H(-)] for dioxane, THF, and Et2O as ethers, we investigate the manifestation of SSLB-type (short, strong, low -barrier) hydrogen bonding in the OHO motif of an oxonium cation.

Place, publisher, year, edition, pages
2018. Vol. 122, no 15, p. 3713-3727
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-156725DOI: 10.1021/acs.jpca.7b11851ISI: 000430783700001PubMedID: 29589923OAI: oai:DiVA.org:su-156725DiVA, id: diva2:1220199
Available from: 2018-06-18 Created: 2018-06-18 Last updated: 2018-06-18Bibliographically approved

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