Home > Publications database > Investigation of Structural Changes of Cu(I) and Ag(I) Complexes Utilizing a Flexible, Yet Sterically Demanding Multidentate Phosphine Oxide Ligand > print

001     893384
005     20240725202006.0
024 7 _ |a 10.1021/acs.inorgchem.0c03334
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024 7 _ |a 1520-510X
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024 7 _ |a 2128/28093
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024 7 _ |a 33534576
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037 _ _ |a FZJ-2021-02725
082 _ _ |a 540
100 1 _ |a Kirst, Christin
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245 _ _ |a Investigation of Structural Changes of Cu(I) and Ag(I) Complexes Utilizing a Flexible, Yet Sterically Demanding Multidentate Phosphine Oxide Ligand
260 _ _ |a Washington, DC
|c 2021
|b American Chemical Society
336 7 _ |a article
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520 _ _ |a 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.
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700 1 _ |a Zoller, Florian
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700 1 _ |a Bräuniger, Thomas
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700 1 _ |a Mayer, Peter
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700 1 _ |a Fattakhova-Rohlfing, Dina
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700 1 _ |a Karaghiosoff, Konstantin
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773 _ _ |a 10.1021/acs.inorgchem.0c03334
|g Vol. 60, no. 4, p. 2437 - 2445
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|t Inorganic chemistry
|v 60
|y 2021
|x 1520-510X
856 4 _ |u https://juser.fz-juelich.de/record/893384/files/JACS%20CuAg%20Template_final.pdf
|y Published on 2021-02-03. Available in OpenAccess from 2022-02-03.
856 4 _ |u https://juser.fz-juelich.de/record/893384/files/acs.inorgchem.0c03334-1.pdf
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856 4 _ |u https://juser.fz-juelich.de/record/893384/files/ic0c03334_si_001.pdf
|y Published on 2021-02-03. Available in OpenAccess from 2022-02-03.
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