@article{doi:10.1021/jacs.3c10250,
author = {Miwa, Kazuki and Yokota, Tomoya and Wang, Qian and Sakurai, Takahiro and Fliegl, Heike and Sundholm, Dage and Shinokubo, Hiroshi},
title = {Metallaantiaromaticity of 10-Platinacorrole Complexes},
journal = {Journal of the American Chemical Society},
volume = {146},
number = {2},
pages = {1396-1402},
year = {2024},
doi = {10.1021/jacs.3c10250},
    note ={PMID: 38172072},

URL = { 
    
        https://doi.org/10.1021/jacs.3c10250
    
    

},
eprint = { 
    
        https://doi.org/10.1021/jacs.3c10250
    
    

}
,
    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 a distinct antiaromatic character due to its highly planar conformation. Detailed density functional theory (DFT) calculations revealed that two d orbitals are involved in macrocyclic π-conjugation. We furthermore demonstrated that Craig–Möbius antiaromaticity is not present in the studied system. The synthesis of 10-platinacorroles enables a systematic comparison of the antiaromaticity and aromaticity of closely related porphyrin analogues, providing a better understanding of π-conjugation that involves d orbitals. }
}