Metal complexes with N-heterocyclic carbene (NHC) ligands have been widely used in catalytic chemistry and are now increasingly considered for the development of new chemical tools and metal based drugs. Ruthenium complexes of the type (p-cymene)(NHC)RuCl2 interacted with biologically relevant thiols and selenols, which resulted in the inhibition of enzymes such as thioredoxin reductase or cathepsin B. Pronounced antiproliferative effects could be obtained provided that an appropriate cellular uptake was achieved. Inhibition of tumor cell growth was accompanied by a perturbation of metabolic parameters such as cellular respiration.
6 April 2020 in Physical Chemistry Chemical Physics
The induced magnetic field of C2N (N = 3-14) carbon rings was dissected to contributions from out-of-plane and in-plane π orbitals revealing two concurrent long-range shielding or deshielding cones as a manifestation of the dual aromatic and antiaromatic character of C4n+2 and of C4n rings respectively. Aromaticity based on the magnetic criterion was evaluated with regard to bonding pattern and geometrical characteristics elucidating the influence of bond length and bond angle alternation on out-of-plane and in-plane magnetic response. Ground state polyynic geometries of C4n+2 rings exhibit comparable shielding cones to annulenes, decreasing magnetic response with regard to ring size and similar πout and πin diatropicity. Transition state cumulenic rings display increased aromaticity expressed by a constant very strong magnetic response and augmented πout diatropicity with regard to πin. The variations of the induced magnetic field are explained on the basis of frontier orbital interactions through rotational excitations, which enable further rationalization of the aromatic/antiaromatic behavior.
18 April 2017 in Physical Chemistry Chemical Physics
A direct correlation between π- and spherical aromaticity of the aromatic structures was established by showing that they shared a characteristic shielding cone, resulting from a specific orientation of the applied field. Herein, we revealed the presence of a related long-range shielding cone in spherical aromatic species that was demonstrated through C20, C32, C50, and C60 Hirsh aromatic fullerenes. It was found that while for planar aromatics, the cone is reserved only for a perpendicularly applied field, for spherical aromatic compounds, the three-dimensional cage allows the formation of a shielding cone according to the given orientation of the external field.
15 November 2013 in Chemistry – A European Journal