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H-2 Cleavage by Frustrated Lewis Pairs Characterized by the Energy Decomposition Analysis of Transition States: An Alternative to the Electron Transfer and Electric Field Models
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 36, p. 7202-7211Article in journal (Refereed) Published
Abstract [en]

Knowing that the Papai's electron transfer (ET) and the Grimme's electric field (EF) models draw attention to somewhat different physical aspects, we are going to systematically (re)examine interactions in the transition states (TSs) of the heterolytic H-2-cleavage by the Frustrated Lewis Pairs (FLPs). Our main vehicle is the quantitative energy decomposition analysis (EDA), a powerful method for elucidation of interactions, plus the analysis of molecular orbitals (MOs). Herein, the Lewis acid (LA) is B(C6F5)(3) and the Lewis bases (LBs) are tBu(3)P, (o-C6H4Me)(3)P, 2,6-lutidine, 2,4,6-lutidine, MeN=C(Ph)Me imine, MeN(H)-C(H)PhMe amine, THF, 1,4-dioxane, and acetone. For a series of the phosphorus-, nitrogen-, and oxygen-bearing LBs plus B(C6F5)(3), we will show that (i) neither the electrostatic nor the orbital interactions dominate but instead both are essential alongside the Pauli repulsion and (ii) the frontier molecular orbitals (FMOs) of a TS can arise not only from the push-pull molecular orbital scheme by Papai et al., which directly involves the occupied sigma and the empty sigma* MOs of H-2, but also from a more intricate but energetically more fitting orbital interactions which have escaped notice thus far.

Place, publisher, year, edition, pages
2018. Vol. 122, no 36, p. 7202-7211
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-161050DOI: 10.1021/acs.jpca.8b06830ISI: 000444924000009PubMedID: 30107109OAI: oai:DiVA.org:su-161050DiVA, id: diva2:1256163
Available from: 2018-10-16 Created: 2018-10-16 Last updated: 2018-10-16Bibliographically approved

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