Reductive Binding and Ligand-Based Redox Transformations of Nitrosobenzene at a Dinickel(II) Core
| Autor: | Sebastian Dechert, Eleonora Ferretti, Franc Meyer |
|---|---|
| Rok vydání: | 2019 |
| Předmět: |
Cryptand
chemistry.chemical_element Pyrazole Ligands 010402 general chemistry 01 natural sciences Catalysis law.invention Inorganic Chemistry Nitrosobenzene chemistry.chemical_compound Nickel law Physical and Theoretical Chemistry Furans Electron paramagnetic resonance Bimetallic strip Density Functional Theory Lewis Acids Binding Sites 010405 organic chemistry 3. Good health 0104 chemical sciences Crystallography chemistry Thermodynamics Spectrophotometry Ultraviolet Density functional theory Protons Oxidation-Reduction Nitroso Compounds |
| Zdroj: | Inorganic Chemistry. 58:5154-5162 |
| ISSN: | 1520-510X 0020-1669 |
| Popis: | The metal-mediated activation of PhNO represents an important starting point for understanding the reactivity patterns of nitrosoarenes in biological systems and catalysis. Here we report that the pyrazole-based dinickel(II) dihydride complex [KL(NiH)2] (1) reacts with PhNO to eliminate dihydrogen concomitant with binding of the doubly reduced substrate in μ-κ(O):κ(N) mode in the bimetallic pocket of [KLNi2(PhNO)] (2). The addition of [2,2,2]cryptand leads to the ionic complex [K(crypt)][LNi2(PhNO)] (3). Structural and spectroscopic analyses evidence that interaction with the Lewis acidic K+ in 2 causes significant elongation and weakening of the substrate’s N–O bond [dN–O = 1.487(12) A in 2 vs 1.374(4) A in 3]. Complex 2 (or 3) reacts with [FeCp*2][PF6] to give LNi2(PhNO) (4), which is shown by electron paramagnetic resonance and IR spectroscopies and density functional theory calculations to feature two low-spin d8 nickel(II) ions and a bridging (PhNO)•– radical anion ligand, with the out-of-plane π*(NO... |
| Databáze: | OpenAIRE |
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