Investigation of Structural Changes of Cu(I) and Ag(I) Complexes Utilizing a Flexible, Yet Sterically Demanding Multidentate Phosphine Oxide Ligand
| Autor: | Konstantin Karaghiosoff, Thomas Bräuniger, Peter Mayer, Dina Fattakhova-Rohlfing, Christin Kirst, Florian Zoller |
|---|---|
| Rok vydání: | 2021 |
| Předmět: |
chemistry.chemical_classification
Phosphine oxide Denticity 010405 organic chemistry Ligand Oxide Nuclear magnetic resonance spectroscopy 010402 general chemistry 01 natural sciences 0104 chemical sciences Coordination complex Inorganic Chemistry chemistry.chemical_compound Crystallography chemistry Phenylphosphine ddc:540 Physical and Theoretical Chemistry Methylene Elektrotechnik |
| Zdroj: | Inorganic chemistry 60(4), 2437-2445 (2021). doi:10.1021/acs.inorgchem.0c03334 |
| ISSN: | 1520-510X |
| DOI: | 10.1021/acs.inorgchem.0c03334 |
| Popis: | The syntheses of a sterically demanding, multidentate bis(quinaldinyl)phenylphosphine oxide ligand and some Cu(I) and Ag(I) complexes thereof are described. By introducing a methylene group between the quinoline unit and phosphorus, the phosphine oxide ligand gains additional flexibility. This specific ligand design induces not only a versatile coordination chemistry but also a rarely observed and investigated behavior in solution. The flexibility of the birdlike ligand offers the unexpected opportunity of open-wing and closed-wing coordination to the metal. In fact, the determined crystal structures of these complexes show both orientations. Investigations of the ligand in solution show a strong dependency of the chemical shift of the CH2 protons on the solvent used. Variable-temperature, multinuclear NMR spectroscopy was carried out, and an interesting dynamic behavior of the complexes is observed. Due to the introduced flexibility, the quinaldinyl substituents change their arrangements from open-wing to closed-wing upon cooling, while still staying coordinated to the metal. This change in conformation is completely reversible when warming up the sample. Based on 2D NMR spectra measured at -80 °C, an assignment of the signals corresponding to the different arrangements was possible. Additionally, the copper(I) complex shows reversible redox activity in solution. The combination of structural flexibility of a multidentate ligand and the positive redox properties of the resulting complexes comprises key factors for a possible application of such compounds in transition-metal catalysis. Via a reorganization of the ligand, occurring transition states could be stabilized, and selectivity might be enhanced. |
| Databáze: | OpenAIRE |
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