DOI: 10.1002/anie.201410637. Electron Flow in Reaction Mechanisms

Electron Flow in Reaction Mechanisms—Revealed from First Principles

10.1002/anie.201410637

Crossref journal-article

Wiley

Angewandte Chemie International Edition (311)

Abstract

AbstractThe “curly arrow” of Robinson and Ingold is the primary tool for describing and rationalizing reaction mechanisms. Despite this approach’s ubiquity and stellar success, its physical basis has never been clarified and a direct connection to quantum chemistry has never been found. Here we report that the bond rearrangements expressed by curly arrows can be directly observed in ab initio computations, as transformations of intrinsic bond orbitals (IBOs) along the reaction coordinate. Our results clarify that curly arrows are rooted in physical reality—a notion which has been challenged before—and show how quantum chemistry can directly establish reaction mechanisms in intuitive terms and unprecedented detail.

Bibliography

Knizia, G., & Klein, J. E. M. N. (2015). Electron Flow in Reaction MechanismsâRevealed from First Principles. Angewandte Chemie International Edition, 54(18), 5518â5522. Portico.

Authors 2

Gerald Knizia (first)
Johannes E. M. N. Klein (additional)

References 57 Referenced 441

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{'key': 'e_1_2_2_44_2', 'volume-title': 'Atoms in molecules: A quantum theory', 'author': 'Bader R. F.', 'year': '1994'} / Atoms in molecules: A quantum theory by Bader R. F. (1994)
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Dates

Type	When
Created	10 years, 5 months ago (March 3, 2015, 3:16 p.m.)
Deposited	1 year, 10 months ago (Oct. 6, 2023, 2:45 p.m.)
Indexed	3 days, 3 hours ago (Aug. 20, 2025, 8:22 a.m.)
Issued	10 years, 5 months ago (March 3, 2015)
Published	10 years, 5 months ago (March 3, 2015)
Published Online	10 years, 5 months ago (March 3, 2015)
Published Print	10 years, 3 months ago (April 27, 2015)

Funders 1

ERC
Awards1
1. 320723

BibTeX

@article{Knizia_2015, title={Electron Flow in Reaction Mechanisms—Revealed from First Principles}, volume={54}, ISSN={1521-3773}, url={http://dx.doi.org/10.1002/anie.201410637}, DOI={10.1002/anie.201410637}, number={18}, journal={Angewandte Chemie International Edition}, publisher={Wiley}, author={Knizia, Gerald and Klein, Johannes E. M. N.}, year={2015}, month=mar, pages={5518–5522} }

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