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oai:docta.ucm.es:20.500.14352/1051952025-09-18T14:42:39Zcom_20.500.14352_14col_20.500.14352_15

Origin of the Bürgi-Dunitz Angle Rodríguez, Humberto A. Bickelhaupt, F. Matthias Fernández López, Israel 547 Bürgi-Dunitz angle Nucleophilic addition Carbonyl Pauli repulsion Density functional calculations Química orgánica (Química) 2306 Química Orgánica The Bürgi-Dunitz (BD) angle plays a pivotal role in organic chemistry to rationalize the nucleophilic addition to carbonyl groups. Yet, the origin of the obtuse trajectory of the nucleophile remains incompletely understood. Herein, we quantify the importance of the underlying physical factors quantum chemically. The obtuse BD angle appears to originate from the concerted action of a reduced Pauli repulsion between the nucleophile HOMO and carbonyl π bond, a more stabilizing HOMO-π*-LUMO(C=O) interaction, as well as a more favorable electrostatic attraction. Ministerio de Ciencia e Innovación (España) Depto. de Química Orgánica Fac. de Ciencias Químicas TRUE pub APC financiada por la UCM 2024-06-24T11:31:50Z 2024-06-24T11:31:50Z 2023 journal article VoR https://hdl.handle.net/20.500.14352/105195 1439-4235 10.1002/cphc.202300379 1439-7641 eng info:eu-repo/grantAgreement/MCIN/AEI/10.13039/501100011033 H. A. Rodríguez, F. M. Bickelhaupt, I. Fernández, ChemPhysChem 2023, 24, e202300379. Attribution 4.0 International http://creativecommons.org/licenses/by/4.0/ open access application/pdf Wiley