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Description of the Reaction Intermediate Stabilization for the Zimmerman Di-π-methane Rearrangement on the Basis of a Parametric Diabatic Analysis

Ortega, Daniela E. and Matute, Ricardo A. (2020) Description of the Reaction Intermediate Stabilization for the Zimmerman Di-π-methane Rearrangement on the Basis of a Parametric Diabatic Analysis. Journal of Physical Chemistry A, 124 (18). pp. 3573-3580. ISSN 1089-5639. https://resolver.caltech.edu/CaltechAUTHORS:20200427-091417649

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Abstract

The mechanism of the Zimmerman di-π-methane rearrangement has been studied using a parametric diabatic analysis (PDA) on which the diagonal elements on the effective Hamiltonian defining the energies of the diabatic electronic states have been parametrized and modeled upon the use of the vertex form of a parabolic function. The PDA requires two inputs: the energy local minimum of an optimized structure along the intrinsic reaction coordinate and the maximum gradients associated with the barriers for the transition states. In the present work, the PDA was used to gain novel insights into the mechanism of the triplet di-π-methane rearrangement of substituted dibenzobarrelenes. Our results suggest that, when using an electron-withdrawing group as substituent, the activation energy for the rate-determining step is directly modulated by the stabilization of the biradical intermediate on the triplet surface. This mechanistic feature was thoroughly analyzed and discussed within the conceptual framework provided by the diabatic model of intermediate stabilization (DMIS).


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.jpca.0c01145DOIArticle
ORCID:
AuthorORCID
Ortega, Daniela E.0000-0002-0724-4206
Matute, Ricardo A.0000-0002-0644-3799
Additional Information:© 2020 American Chemical Society. Received: February 10, 2020; Revised: April 11, 2020; Published: April 14, 2020. Published as part of The Journal of Physical Chemistry virtual special issue “Paul Geerlings Festschrift”. This work is dedicated to Professor Paul Geerlings on the occasion of his 70th birthday. We have been inspired by his pioneering work in the development and application of chemical concepts from the Density Functional Theory. D.E.O. acknowledges the financial support from the Postdoctoral FONDECYT Grant No. 3190252, and R.A.M acknowledges the FONDECYT Grant No. 1181260. Calculations were performed on computational resources supported by the FONDEQUIP Grant EQM 180180. This research was also supported by Anillo Grant ACT192175. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Fondo Nacional de Desarrollo Científico y Tecnológico (FONDECYT)3190252
Fondo Nacional de Desarrollo Científico y Tecnológico (FONDECYT)1181260
Comisión Nacional de Investigación Científica y Tecnológica (CONICYT)EQM 180180
Comisión Nacional de Investigación Científica y Tecnológica (CONICYT)ACT192175
Issue or Number:18
Record Number:CaltechAUTHORS:20200427-091417649
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200427-091417649
Official Citation:Description of the Reaction Intermediate Stabilization for the Zimmerman Di-π-methane Rearrangement on the Basis of a Parametric Diabatic Analysis. Daniela E. Ortega and Ricardo A. Matute. The Journal of Physical Chemistry A 2020 124 (18), 3573-3580; DOI: 10.1021/acs.jpca.0c01145
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:102791
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:27 Apr 2020 16:22
Last Modified:11 May 2020 21:37

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