Unexpected Molecular Structure of a Putative Rhenium‐Dioxo‐Benzocarbaporphyrin Complex. Implications for the Highest Transition Metal Valence in a Porphyrin‐Type Ligand Environment
Abstract A combination of quantum chemical calculations and synthetic studies was used to address the possibility of very high (>6) valence states of transition metals in porphyrin‐type complexes. With corrole as a supporting ligand, DFT calculations ruled out Re(VII) and Ir(VII) dioxo complexes...
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| Format: | Article |
| Language: | English |
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Wiley-VCH
2019-10-01
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| Series: | ChemistryOpen |
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| Online Access: | https://doi.org/10.1002/open.201900271 |
| _version_ | 1819297803799625728 |
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| author | Dr. Abraham B. Alemayehu Dr. Hugo Vazquez‐Lima Dr. Simon J. Teat Prof. Dr. Abhik Ghosh |
| author_facet | Dr. Abraham B. Alemayehu Dr. Hugo Vazquez‐Lima Dr. Simon J. Teat Prof. Dr. Abhik Ghosh |
| author_sort | Dr. Abraham B. Alemayehu |
| collection | DOAJ |
| description | Abstract A combination of quantum chemical calculations and synthetic studies was used to address the possibility of very high (>6) valence states of transition metals in porphyrin‐type complexes. With corrole as a supporting ligand, DFT calculations ruled out Re(VII) and Ir(VII) dioxo complexes as stable species. Attempted rhenium insertion into benzocarbaporphyrin (BCP) ligands on the other hand led to two products with different stoichiometries – Re[BCP]O and Re[BCP]O2. To our surprise, single‐crystal structure determination of one of the complexes of the latter type indicated an ReVO center with a second oxygen bridging the Re−C bond. In other words, although the monooxo complexes Re[BCP]O are oxophilic, the BCP ligand cannot sustain a trans‐ReVII(O)2 center. The search for metal valence states >6 in porphyrin‐type ligand environments must therefore continue. |
| first_indexed | 2024-12-24T05:19:49Z |
| format | Article |
| id | doaj.art-8a9919426e484435a04b66a3b61e6f38 |
| institution | Directory Open Access Journal |
| issn | 2191-1363 |
| language | English |
| last_indexed | 2024-12-24T05:19:49Z |
| publishDate | 2019-10-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | ChemistryOpen |
| spelling | doaj.art-8a9919426e484435a04b66a3b61e6f382022-12-21T17:13:29ZengWiley-VCHChemistryOpen2191-13632019-10-018101298130210.1002/open.201900271Unexpected Molecular Structure of a Putative Rhenium‐Dioxo‐Benzocarbaporphyrin Complex. Implications for the Highest Transition Metal Valence in a Porphyrin‐Type Ligand EnvironmentDr. Abraham B. Alemayehu0Dr. Hugo Vazquez‐Lima1Dr. Simon J. Teat2Prof. Dr. Abhik Ghosh3Department of Chemistry UiT – The Arctic University of Norway 9037 Tromsø NorwayCentro de Química, Instituto de Ciencias Universidad Autónoma de Puebla Edif. IC9, CU, San Manuel 72570 Puebla, Puebla MexicoAdvanced Light Source Lawrence Berkeley National Laboratory Berkeley CA 94720–8229 USADepartment of Chemistry UiT – The Arctic University of Norway 9037 Tromsø NorwayAbstract A combination of quantum chemical calculations and synthetic studies was used to address the possibility of very high (>6) valence states of transition metals in porphyrin‐type complexes. With corrole as a supporting ligand, DFT calculations ruled out Re(VII) and Ir(VII) dioxo complexes as stable species. Attempted rhenium insertion into benzocarbaporphyrin (BCP) ligands on the other hand led to two products with different stoichiometries – Re[BCP]O and Re[BCP]O2. To our surprise, single‐crystal structure determination of one of the complexes of the latter type indicated an ReVO center with a second oxygen bridging the Re−C bond. In other words, although the monooxo complexes Re[BCP]O are oxophilic, the BCP ligand cannot sustain a trans‐ReVII(O)2 center. The search for metal valence states >6 in porphyrin‐type ligand environments must therefore continue.https://doi.org/10.1002/open.201900271corrolebenzocarbaporphyrinrheniumiridiumhigh-valent compounds |
| spellingShingle | Dr. Abraham B. Alemayehu Dr. Hugo Vazquez‐Lima Dr. Simon J. Teat Prof. Dr. Abhik Ghosh Unexpected Molecular Structure of a Putative Rhenium‐Dioxo‐Benzocarbaporphyrin Complex. Implications for the Highest Transition Metal Valence in a Porphyrin‐Type Ligand Environment ChemistryOpen corrole benzocarbaporphyrin rhenium iridium high-valent compounds |
| title | Unexpected Molecular Structure of a Putative Rhenium‐Dioxo‐Benzocarbaporphyrin Complex. Implications for the Highest Transition Metal Valence in a Porphyrin‐Type Ligand Environment |
| title_full | Unexpected Molecular Structure of a Putative Rhenium‐Dioxo‐Benzocarbaporphyrin Complex. Implications for the Highest Transition Metal Valence in a Porphyrin‐Type Ligand Environment |
| title_fullStr | Unexpected Molecular Structure of a Putative Rhenium‐Dioxo‐Benzocarbaporphyrin Complex. Implications for the Highest Transition Metal Valence in a Porphyrin‐Type Ligand Environment |
| title_full_unstemmed | Unexpected Molecular Structure of a Putative Rhenium‐Dioxo‐Benzocarbaporphyrin Complex. Implications for the Highest Transition Metal Valence in a Porphyrin‐Type Ligand Environment |
| title_short | Unexpected Molecular Structure of a Putative Rhenium‐Dioxo‐Benzocarbaporphyrin Complex. Implications for the Highest Transition Metal Valence in a Porphyrin‐Type Ligand Environment |
| title_sort | unexpected molecular structure of a putative rhenium dioxo benzocarbaporphyrin complex implications for the highest transition metal valence in a porphyrin type ligand environment |
| topic | corrole benzocarbaporphyrin rhenium iridium high-valent compounds |
| url | https://doi.org/10.1002/open.201900271 |
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