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Octahedral iron(iv)–tosylimido complexes exhibiting single electron-oxidation reactivity† †Electronic supplementary information (ESI) available. CCDC 1918211. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c9sc02526j
| Content Provider | Semantic Scholar |
|---|---|
| Author | Sabenya, Gerard Gamba, Ilaria Gómez, Laura Clémancey, Martin Frisch, Jonathan R. Klinker, Eric Blondin, Geneviève Torelli, Stéphane Que, Lawrence Martin-Diaconescu, Vlad Latour, Jean Marc Lloret-Fillol, Julio Costas, Miquel |
| Copyright Year | 2019 |
| Abstract | High valent iron species are very reactive molecules involved in oxidation reactions of relevance to biology and chemical synthesis. Herein we describe iron(iv)-tosylimido complexes [FeIV(NTs)(MePy2tacn)](OTf)2 (1(IV)[double bond, length as m-dash]NTs) and [FeIV(NTs)(Me2(CHPy2)tacn)](OTf)2 (2(IV)[double bond, length as m-dash]NTs), (MePy2tacn = N-methyl-N,N-bis(2-picolyl)-1,4,7-triazacyclononane, and Me2(CHPy2)tacn = 1-(di(2-pyridyl)methyl)-4,7-dimethyl-1,4,7-triazacyclononane, Ts = Tosyl). 1(IV)[double bond, length as m-dash]NTs and 2(IV)[double bond, length as m-dash]NTs are rare examples of octahedral iron(iv)-imido complexes and are isoelectronic analogues of the recently described iron(iv)-oxo complexes [FeIV(O)(L)]2+ (L = MePy2tacn and Me2(CHPy2)tacn, respectively). 1(IV)[double bond, length as m-dash]NTs and 2(IV)[double bond, length as m-dash]NTs are metastable and have been spectroscopically characterized by HR-MS, UV-vis, 1H-NMR, resonance Raman, Mössbauer, and X-ray absorption (XAS) spectroscopy as well as by DFT computational methods. Ferric complexes [FeIII(HNTs)(L)]2+, 1(III)-NHTs (L = MePy2tacn) and 2(III)-NHTs (L = Me2(CHPy2)tacn) have been isolated after the decay of 1(IV)[double bond, length as m-dash]NTs and 2(IV)[double bond, length as m-dash]NTs in solution, spectroscopically characterized, and the molecular structure of [FeIII(HNTs)(MePy2tacn)](SbF6)2 determined by single crystal X-ray diffraction. Reaction of 1(IV)[double bond, length as m-dash]NTs and 2(IV)[double bond, length as m-dash]NTs with different p-substituted thioanisoles results in the transfer of the tosylimido moiety to the sulphur atom producing sulfilimine products. In these reactions, 1(IV)[double bond, length as m-dash]NTs and 2(IV)[double bond, length as m-dash]NTs behave as single electron oxidants and Hammett analyses of reaction rates evidence that tosylimido transfer is more sensitive than oxo transfer to charge effects. In addition, reaction of 1(IV)[double bond, length as m-dash]NTs and 2(IV)[double bond, length as m-dash]NTs with hydrocarbons containing weak C-H bonds results in the formation of 1(III)-NHTs and 2(III)-NHTs respectively, along with the oxidized substrate. Kinetic analyses indicate that reactions proceed via a mechanistically unusual HAT reaction, where an association complex precedes hydrogen abstraction. |
| Starting Page | 9513 |
| Ending Page | 9529 |
| Page Count | 17 |
| File Format | PDF HTM / HTML |
| PubMed reference number | 32055323 |
| Journal | Medline |
| Volume Number | 10 |
| Alternate Webpage(s) | http://www.rsc.org/suppdata/c9/sc/c9sc02526j/c9sc02526j1.pdf |
| Alternate Webpage(s) | https://doi.org/10.1039/c9sc02526j |
| Journal | Chemical science |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
