Origin of the Enhanced Binding Capability toward Axial Nitrogen Bases of Ni(II) Porphyrins Bearing Electron-Withdrawing Substituents: An Electronic Structure and Bond Energy Analysis

Mario Amati, Evert Jan Baerends, Giampaolo Ricciardi*, Angela Rosa

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Axial coordination to metalloporphyrins is important in many biological and catalytic processes. Experiments found the axial coordination of nitrogenous bases to nickel(II) porphyrins to be strongly favored by electron-withdrawing substituents such as perfluorophenyls at the meso carbon positions. Careful analysis of the electronic structure reveals that the natural explanation in terms of density change of the nickel(II) porphyrin system (in particular the metal), does not apply. Electron density changes, by the assumed inductive or polarizing effects on the metal or on the porphyrin ring system, are slight. The effect is caused by a remarkable through-space electric field effect on the metalloporphyrin system, originating from the charge distribution inside the perfluorphenyl groups (mostly the C-F dipoles).

Original languageEnglish
Pages (from-to)11528-11541
Number of pages14
JournalInorganic Chemistry
Volume59
Issue number16
Early online date29 Jul 2020
DOIs
Publication statusPublished - 17 Aug 2020

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