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@ARTICLE{Kirst:893384,
author = {Kirst, Christin and Zoller, Florian and Bräuniger, Thomas
and Mayer, Peter and Fattakhova-Rohlfing, Dina and
Karaghiosoff, Konstantin},
title = {{I}nvestigation of {S}tructural {C}hanges of {C}u({I}) and
{A}g({I}) {C}omplexes {U}tilizing a {F}lexible, {Y}et
{S}terically {D}emanding {M}ultidentate {P}hosphine {O}xide
{L}igand},
journal = {Inorganic chemistry},
volume = {60},
number = {4},
issn = {1520-510X},
address = {Washington, DC},
publisher = {American Chemical Society},
reportid = {FZJ-2021-02725},
pages = {2437 - 2445},
year = {2021},
abstract = {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.},
cin = {IEK-1},
ddc = {540},
cid = {I:(DE-Juel1)IEK-1-20101013},
pnm = {1232 - Power-based Fuels and Chemicals (POF4-123)},
pid = {G:(DE-HGF)POF4-1232},
typ = {PUB:(DE-HGF)16},
pubmed = {33534576},
UT = {WOS:000620345400035},
doi = {10.1021/acs.inorgchem.0c03334},
url = {https://juser.fz-juelich.de/record/893384},
}