Oxidation-Induced Detachment of Ruthenoarene Units and Oxygen Insertion in Bis-Pd(II) Hexaphyrin π-Ruthenium Complexes

Two types of new bis-Pd(II) hexaphyrin π-ruthenium complexes are reported. A double-decker bis-Pd(II) hexaphyrin π-ruthenium complex <b>4</b> was obtained by oxidation-induced detachment of a ruthenoarene unit from the triple-decker complex <b>3</b> and oxygen-inserted triple...

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Main Authors:	Akito Nakai, Takayuki Tanaka, Atsuhiro Osuka
Format:	Article
Language:	English
Published:	MDPI AG 2020-06-01
Series:	Molecules
Subjects:	expanded porphyrin π-complex ruthenium complex aromaticity
Online Access:	https://www.mdpi.com/1420-3049/25/12/2753

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spelling	doaj-e4daa6d10bea4f42a7a0daad79e2d24c2020-11-25T03:14:56ZengMDPI AGMolecules1420-30492020-06-01252753275310.3390/molecules25122753Oxidation-Induced Detachment of Ruthenoarene Units and Oxygen Insertion in Bis-Pd(II) Hexaphyrin π-Ruthenium ComplexesAkito Nakai0Takayuki Tanaka1Atsuhiro Osuka2Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502, JapanDepartment of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502, JapanDepartment of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502, JapanTwo types of new bis-Pd(II) hexaphyrin π-ruthenium complexes are reported. A double-decker bis-Pd(II) hexaphyrin π-ruthenium complex <b>4</b> was obtained by oxidation-induced detachment of a ruthenoarene unit from the triple-decker complex <b>3</b> and oxygen-inserted triple-decker bis-Pd(II) hexaphyrin π-ruthenium complex <b>6</b> was obtained upon treatment of bis-Pd(II) [26]hexaphyrin <b>5</b> with [RuCl<sub>2</sub>(<i>p</i>-cymene)]<sub>2</sub> under aerobic conditions. Although π-metal complexation of porphyrinoids often results in decreased global aromaticity due to the enhancement of local 6π aromatic segments, distinct aromatic characters were indicated for <b>4</b> and <b>6</b> by <sup>1</sup>H-NMR spectral and theoretical calculations. These results are accounted for in terms of possible resonance contributors of hexaphyrin di- and tetraanion ligands. Thus, π-metal coordination has been shown to be effective for modulation of the overall aromaticity.https://www.mdpi.com/1420-3049/25/12/2753expanded porphyrinπ-complexruthenium complexaromaticity
collection	DOAJ
language	English
format	Article
sources	DOAJ
author	Akito Nakai Takayuki Tanaka Atsuhiro Osuka
spellingShingle	Akito Nakai Takayuki Tanaka Atsuhiro Osuka Oxidation-Induced Detachment of Ruthenoarene Units and Oxygen Insertion in Bis-Pd(II) Hexaphyrin π-Ruthenium Complexes Molecules expanded porphyrin π-complex ruthenium complex aromaticity
author_facet	Akito Nakai Takayuki Tanaka Atsuhiro Osuka
author_sort	Akito Nakai
title	Oxidation-Induced Detachment of Ruthenoarene Units and Oxygen Insertion in Bis-Pd(II) Hexaphyrin π-Ruthenium Complexes
title_short	Oxidation-Induced Detachment of Ruthenoarene Units and Oxygen Insertion in Bis-Pd(II) Hexaphyrin π-Ruthenium Complexes
title_full	Oxidation-Induced Detachment of Ruthenoarene Units and Oxygen Insertion in Bis-Pd(II) Hexaphyrin π-Ruthenium Complexes
title_fullStr	Oxidation-Induced Detachment of Ruthenoarene Units and Oxygen Insertion in Bis-Pd(II) Hexaphyrin π-Ruthenium Complexes
title_full_unstemmed	Oxidation-Induced Detachment of Ruthenoarene Units and Oxygen Insertion in Bis-Pd(II) Hexaphyrin π-Ruthenium Complexes
title_sort	oxidation-induced detachment of ruthenoarene units and oxygen insertion in bis-pd(ii) hexaphyrin π-ruthenium complexes
publisher	MDPI AG
series	Molecules
issn	1420-3049
publishDate	2020-06-01
description	Two types of new bis-Pd(II) hexaphyrin π-ruthenium complexes are reported. A double-decker bis-Pd(II) hexaphyrin π-ruthenium complex <b>4</b> was obtained by oxidation-induced detachment of a ruthenoarene unit from the triple-decker complex <b>3</b> and oxygen-inserted triple-decker bis-Pd(II) hexaphyrin π-ruthenium complex <b>6</b> was obtained upon treatment of bis-Pd(II) [26]hexaphyrin <b>5</b> with [RuCl<sub>2</sub>(<i>p</i>-cymene)]<sub>2</sub> under aerobic conditions. Although π-metal complexation of porphyrinoids often results in decreased global aromaticity due to the enhancement of local 6π aromatic segments, distinct aromatic characters were indicated for <b>4</b> and <b>6</b> by <sup>1</sup>H-NMR spectral and theoretical calculations. These results are accounted for in terms of possible resonance contributors of hexaphyrin di- and tetraanion ligands. Thus, π-metal coordination has been shown to be effective for modulation of the overall aromaticity.
topic	expanded porphyrin π-complex ruthenium complex aromaticity
url	https://www.mdpi.com/1420-3049/25/12/2753
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Oxidation-Induced Detachment of Ruthenoarene Units and Oxygen Insertion in Bis-Pd(II) Hexaphyrin π-Ruthenium Complexes

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