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Rhenium-Imido Corroles
| Content Provider | Scilit |
|---|---|
| Author | Alemayehu, Abraham B. Teat, Simon J. Borisov, Sergey M. Ghosh, Abhik |
| Copyright Year | 2020 |
| Abstract | Metallocorroles involving 5d transition metals are currently of interest as near-IR phosphors and as photosensitizers for oxygen sensing and photodynamic therapy. Their syntheses, however, are often bedeviled by capricious and low-yielding protocols. Against this backdrop, we describe rhenium-imido corroles, a new class of 5d metallocorroles, synthesized simply and in respectable (∼30%) yields via the interaction of a free-base corrole, $Re_{2}(CO)_{10}$, $K_{2}CO_{3}$, and aniline in 1,2,4-trichlorobenzene at ∼190 °C in a sealed vial under strict anaerobic conditions. The generality of the method was shown by the synthesis of six derivatives, including those derived from meso-tris(pentafluorophenyl)corrole, $H_{3}$[TPFPC], and five different meso-tris(p-X-phenyl)corroles, $H_{3}$[TpXPC], where X = $CF_{3}$, F, H, $CH_{3}$, $OCH_{3}$. Single-crystal X-ray structures obtained for two of the complexes, Re[TpFPC](NPh) and $Re[TpCF_{3}$PC](NPh), revealed relatively unstrained equatorial Re–N distances of ∼2.00 Å, a ∼ 0.7-Å displacement of the Re from the mean plane of the corrole nitrogens, and an $Re–N_{imido}$ distance of ∼1.72 Å. Details of the corrole skeletal bond distances, diamagnetic$ ^{1}$H NMR spectra, relatively substituent-independent Soret maxima, and electrochemical HOMO–LUMO gaps of ∼2.2 V all indicated an innocent corrole macrocycle. Surprisingly, unlike several other classes of 5d metallocorroles, the Re-imido complexes proved nonemissive in solution at room temperature and also failed to sensitize singlet oxygen formation, indicating rapid radiationless deactivation of the triplet state, presumably via the rapidly rotating axial phenyl group. By analogy with other metal-oxo and -imido corroles, we remain hopeful that the Re-imido group will prove amenable to further elaboration and thereby contribute to the development of a somewhat challenging area of coordination chemistry. |
| Related Links | https://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.0c00477 https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7311055/pdf |
| Ending Page | 6389 |
| Page Count | 8 |
| Starting Page | 6382 |
| ISSN | 00201669 |
| e-ISSN | 1520510X |
| DOI | 10.1021/acs.inorgchem.0c00477 |
| Journal | Inorganic Chemistry |
| Issue Number | 9 |
| Volume Number | 59 |
| Language | English |
| Publisher | American Chemical Society (ACS) |
| Publisher Date | 2020-04-10 |
| Access Restriction | Open |
| Subject Keyword | Journal: Inorganic Chemistry Inorganic Chemistry 5d Metallocorroles Class of 5d |
| Content Type | Text |
| Resource Type | Article |
| Subject | Physical and Theoretical Chemistry Inorganic Chemistry |
