Metallaantiaromaticity of 10-Platinacorrole Complexes

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2024 Jan 3

PMID 38172072

Authors

Kazuki Miwa

Tomoya Yokota

Qian Wang

Takahiro Sakurai

Heike Fliegl

Dage Sundholm

Hiroshi Shinokubo

Affiliations

Soon will be listed here.

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.

References

Juselius J, Sundholm D, Gauss J . Calculation of current densities using gauge-including atomic orbitals. J Chem Phys. 2004; 121(9):3952-63. DOI: 10.1063/1.1773136. View

Casida M, Huix-Rotllant M . Progress in time-dependent density-functional theory. Annu Rev Phys Chem. 2012; 63:287-323. DOI: 10.1146/annurev-physchem-032511-143803. View

Umasekhar B, Shetti V, Ravikanth M . Heterocorroles: corrole analogues containing heteroatom(s) in the core or at a -position. RSC Adv. 2022; 8(38):21100-21132. PMC: 9080920. DOI: 10.1039/c8ra03669a. View

Horie M, Hayashi Y, Yamaguchi S, Shinokubo H . Synthesis of nickel(II) azacorroles by Pd-catalyzed amination of α,α'-dichlorodipyrrin Ni(II) complex and their properties. Chemistry. 2012; 18(19):5919-23. DOI: 10.1002/chem.201200485. View

Oh J, Sung Y, Hong Y, Kim D . Spectroscopic Diagnosis of Excited-State Aromaticity: Capturing Electronic Structures and Conformations upon Aromaticity Reversal. Acc Chem Res. 2018; 51(6):1349-1358. DOI: 10.1021/acs.accounts.7b00629. View

Sakow D, Boker B, Brandhorst K, Burghaus O, Broring M . 10-Heterocorroles: ring-contracted porphyrinoids with fine-tuned aromatic and metal-binding properties. Angew Chem Int Ed Engl. 2013; 52(18):4912-5. DOI: 10.1002/anie.201300757. View

Zhu C, Luo M, Zhu Q, Zhu J, Schleyer P, I-Chia Wu J . Planar Möbius aromatic pentalenes incorporating 16 and 18 valence electron osmiums. Nat Commun. 2014; 5:3265. DOI: 10.1038/ncomms4265. View

Simkowa I, Latos-Grazynski L, Stepien M . π Conjugation transmitted across a d-electron metallocene in ferrocenothiaporphyrin macrocycles. Angew Chem Int Ed Engl. 2010; 49(42):7665-9. DOI: 10.1002/anie.201004015. View

Fliegl H, Taubert S, Lehtonen O, Sundholm D . The gauge including magnetically induced current method. Phys Chem Chem Phys. 2011; 13(46):20500-18. DOI: 10.1039/c1cp21812c. View

10.

Osuka A, Saito S . Expanded porphyrins and aromaticity. Chem Commun (Camb). 2011; 47(15):4330-9. DOI: 10.1039/c1cc10534e. View

11.

Stepien M, Latos-Grazynski L, Sprutta N, Chwalisz P, Szterenberg L . Expanded porphyrin with a split personality: a Hückel-Möbius aromaticity switch. Angew Chem Int Ed Engl. 2007; 46(41):7869-73. DOI: 10.1002/anie.200700555. View

12.

Chen D, Hua Y, Xia H . Metallaaromatic Chemistry: History and Development. Chem Rev. 2020; 120(23):12994-13086. DOI: 10.1021/acs.chemrev.0c00392. View

13.

Stanger A . What is... aromaticity: a critique of the concept of aromaticity-can it really be defined?. Chem Commun (Camb). 2009; (15):1939-47. DOI: 10.1039/b816811c. View

14.

Tanaka Y, Saito S, Mori S, Aratani N, Shinokubo H, Shibata N . Metalation of expanded porphyrins: a chemical trigger used to produce molecular twisting and Möbius aromaticity. Angew Chem Int Ed Engl. 2007; 47(4):681-4. DOI: 10.1002/anie.200704407. View

15.

Bleeke J . Metallabenzenes. Chem Rev. 2001; 101(5):1205-27. DOI: 10.1021/cr990337n. View

16.

Sundholm D, Dimitrova M, Berger R . Current density and molecular magnetic properties. Chem Commun (Camb). 2021; 57(93):12362-12378. DOI: 10.1039/d1cc03350f. View

17.

Grocka I, Latos-Grazynski L, Stepien M . Ruthenocenoporphyrinoids: conformation determines macrocyclic π conjugation transmitted across a d-electron metallocene. Angew Chem Int Ed Engl. 2012; 52(3):1044-8. DOI: 10.1002/anie.201208289. View

18.

El Bakouri O, Szczepanik D, Jorner K, Ayub R, Bultinck P, Sola M . Three-Dimensional Fully π-Conjugated Macrocycles: When 3D-Aromatic and When 2D-Aromatic-in-3D?. J Am Chem Soc. 2022; 144(19):8560-8575. PMC: 9121391. DOI: 10.1021/jacs.1c13478. View

19.

Merino G, Sola M, Fernandez I, Foroutan-Nejad C, Lazzeretti P, Frenking G . Aromaticity: Quo Vadis. Chem Sci. 2023; 14(21):5569-5576. PMC: 10231312. DOI: 10.1039/d2sc04998h. View

20.

Fernandez I, Frenking G, Merino G . Aromaticity of metallabenzenes and related compounds. Chem Soc Rev. 2015; 44(18):6452-63. DOI: 10.1039/c5cs00004a. View