Metallaantiaromaticity of 10-Platinacorrole Complexes

29 August 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

The aromaticity of cyclic π-conjugated organometallic compounds is known as metallaaromaticity. π-Conjugated metallacycles, such as metallabenzenes and metallapentalenes, have been investigated in order to understand the involvement of the d electrons from the metal center in the π-conjugated systems of the organic ligands. Here, we report the synthesis of Pd(II) 10-platinacorrole complexes with cyclooctadiene (COD) and norbornadiene (NBD) ligands. While the Pd(II) 10-platinacorrole COD complex adopts a distorted structure without showing appreciable antiaromaticity, the corresponding NBD complex exhibits distinct antiaromatic character due to its highly planar conformation. Detailed density-functional-theory (DFT) calculations revealed that two d orbitals are involved in the macrocyclic π-conjugation. We furthermore demonstrated that Craig–Möbius antiaromaticity is not present in the studied system. The synthesis of 10-platinacorroles enables the systematic comparison of the antiaromaticity and aromaticity of closely related porphyrin analogues, providing a better understanding of π-conjugation that involves d orbitals.

Keywords

aromaticity
antiaromaticity
porphyrinoids
conjugation
DFT calculations
d orbital

Supplementary materials

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Title
Metallaantiaromaticity of 10-Platinacorrole Complexes
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