Iron-Catalyzed Activation of Carbon-Halogen Bonds

Eveline H. Tiekink, Henrik Poets, Trevor A. Hamlin*, F. Matthias Bickelhaupt*

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

We have studied the cross-coupling reaction of C(spn)-X bonds (n = 1-3; X = F, Cl, Br, I) mediated by the model iron-d8 catalyst Fe(CO)4 with the archetypal model substrates H3C-CH2-X, H2C═CH-X, and HC≡C-X, utilizing relativistic density functional theory at ZORA-OPBE/TZ2P. The barrier of the oxidative-addition step decreases as the C(spn)-X bond varies from X = F to Cl to Br to I and from C(sp3) to C(sp2) to C(sp). Activation strain and energy decomposition analyses uncover that the lowering of the reaction barrier from X = F to I is caused by (i) a weaker C(spn)-X bond that needs to be broken, (ii) enhanced HOMO-LUMO interactions, and (iii) a stronger electrostatic attraction between the catalyst and the substrate due to the more diffuse electron density and higher nuclear charge of the X atom when varying from X = F to I.

Original languageEnglish
Pages (from-to)36-45
Number of pages10
JournalOrganometallics
Volume44
Issue number1
Early online date25 Oct 2024
DOIs
Publication statusPublished - 13 Jan 2025

Bibliographical note

Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society.

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