Redox Non-Innocence of a N-Heterocyclic Nitrenium Cation Bound to a Nickel–Cyclam Core
| Autor: | Claudio Greco, Florian Felix Pfaff, Florian Heims, Maurizio Bruschi, Erik R. Farquhar, Sarah-Luise Abram, Kallol Ray |
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| Přispěvatelé: | Heims, F, Pfaff, F, Abram, S, Farquhar, E, Bruschi, M, Greco, C, Ray, K |
| Rok vydání: | 2013 |
| Předmět: |
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Molecular Nitrogen Inorganic chemistry chemistry.chemical_element Biochemistry Redox Article Catalysis Formate oxidation chemistry.chemical_compound Colloid and Surface Chemistry Heterocyclic Compounds Nickel Cations Cyclam Organometallic Compounds Molecule Molecular Structure Ligand General Chemistry Crystallography chemistry Nitrenium Cation Functional group Quantum Theory Oxidation-Reduction Derivative (chemistry) |
| Zdroj: | Journal of the American Chemical Society. 136:582-585 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/ja4099559 |
| Popis: | The redox properties of Ni complexes bound to a new ligand, [DMC-nit] +, where a N-heterocyclic nitrenium group is anchored on a 1,4,8,11-tetraazacyclotetradecane backbone, have been examined using spectroscopic and DFT methods. Ligand-based [(DMC-nit)Ni]2+/+ reduction and metal-based [(DMC-nit)Ni]2+/3+ oxidation processes have been established for the [(DMC-nit)Ni]+/2+/3+ redox series, which represents the first examples of nitrenium nitrogen (Nnit)-bound first-row transition-metal complexes. An unprecedented bent binding mode of Nnit in [(DMC-nit)Ni]2+ is observed, which possibly results from the absence of any Nnit→Ni σ-donation. For the corresponding [(DMC-nit)Ni(F)]2+ complex, σ-donation is dominant, and hence a coplanar arrangement at Nnit is predicted by DFT. The binding of the triazolium ion to Ni enables new chemistry (formate oxidation) that is not observed in a derivative that lacks this functional group. Thus the N-heterocyclic nitrenium ligand is a potentially useful and versatile reagent in transition-metal-based catalysis. © 2013 American Chemical Society. |
| Databáze: | OpenAIRE |
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