Nucleophilic versus Electrophilic Reactivity of Bioinspired Superoxido Nickel(II) Complexes
| Autor: | Matthias Driess, Bhawana Pandey, Erik Andris, Teresa Corona, S. Künstner, Chakadola Panda, Jana Roithová, Erik R. Farquhar, Somenath Garai, Kallol Ray, Nils Lindenmaier, Gopalan Rajaraman, Anirban Chandra |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
Models
Molecular chemistry.chemical_element Salt (chemistry) Lithium 010402 general chemistry 01 natural sciences Medicinal chemistry Catalysis Nucleophile Coordination Complexes Nickel Superoxides Spectroscopy and Catalysis Struktur aktivitats beziehungen Reactivity (chemistry) chemistry.chemical_classification 010405 organic chemistry General Medicine General Chemistry 0104 chemical sciences Oxygen chemistry Electrophile Oxygenases Quantum Theory Salts Oxidoreductases Ground state Oxidation-Reduction |
| Zdroj: | Angewandte Chemie. International Edition, 57, 45, pp. 14883-14887 Angewandte Chemie. International Edition, 57, 14883-14887 |
| ISSN: | 1433-7851 |
| DOI: | 10.1002/anie.201808085 |
| Popis: | The formation and detailed spectroscopic characterization of the first biuret-containing monoanionic superoxido-NiII intermediate [LNiO2 ]- as the Li salt [2; L=MeN[C(=O)NAr)2 ; Ar=2,6-iPr2 C6 H3 )] is reported. It results from oxidation of the corresponding [Li(thf)3 ]2 [LNiII Br2 ] complex M with excess H2 O2 in the presence of Et3 N. The [LNiO2 ]- core of 2 shows an unprecedented nucleophilic reactivity in the oxidative deformylation of aldehydes, in stark contrast to the electrophilic character of the previously reported neutral Nacnac-containing superoxido-NiII complex 1, [L'NiO2 ] (L'=CH(CMeNAr)2 ). According to density-functional theory (DFT) calculations, the remarkably different behaviour of 1 versus 2 can be attributed to their different charges and a two-state reactivity, in which a doublet ground state and a nearby spin-polarized doublet excited-state both contribute in 1 but not in 2. The unexpected nucleophilicity of the superoxido-NiII core of 2 suggests that such a reactivity may also play a role in catalytic cycles of Ni-containing oxygenases and oxidases. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|
Plný text