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...
| Main Authors: | , , |
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| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2020-06-01
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| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/25/12/2753 |
| Summary: | 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. |
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| ISSN: | 1420-3049 |