Proton-assisted seven-electron acceptor properties of di-iso-propylphenyl-bis-iminoacenaphthene.

Herein, we report the record-breaking seven-electron reduction of di-iso-propylphenyl-bis-iminoacenaphthene (dpp-bian) involving protons under chemical and electrochemical reduction conditions. Using the dpp-bian-H2 compound as a starting reagent, its mono- and trisodium salts were obtained. A voltammetric study showed that the trinuclear sodium salt can accept an additional seventh electron upon electrochemical reduction.

Hypervalent Sulfur Derivatives as Sulfenylating Reagents: Visible-Light-Mediated Direct Thiolation of Activated C(sp2)-H Bonds with Dihalosulfuranes.

In contrast to hypervalent iodine compounds, the chemistry of their sulfur analogues has been considerably less explored. Herein, we report the direct C-H bond thiolation of electron-rich heterocycles, arenes, and 1,3-dicarbonyls by dichlorosulfuranes under mild conditions. Mechanistic studies and density functional theory calculations suggest the radical chain mechanism of the disclosed transformation. The key to success is attributed to a strikingly low S-Cl bond dissociation energy, which enables the generation of radical species upon exposure to daylight.

Carbon Dioxide Electroreduction and Formic Acid Oxidation by Formal Nickel(I) Complexes of Di-isopropylphenyl Bis-iminoacenaphthene.

Processing CO2 into value-added chemicals and fuels stands as one of the most crucial tasks in addressing the global challenge of the greenhouse effect. In this study, we focused on the complex (dpp-bian)NiBr2 (where dpp-bian is di-isopropylphenyl bis-iminoacenaphthene) as a precatalyst for the electrochemical reduction of CO2 into CH4 as the sole product. Cyclic voltammetry results indicate that the realization of a catalytically effective pattern requires the three-electron reduction of (dpp-bian)NiBr2. The chemically reduced complexes [K(THF)6]+[(dpp-bian)Ni(COD)]- and [K(THF)6]+[(dpp-bian)2Ni]- were synthesized and structurally characterized. Analyzing the data from the electron paramagnetic resonance study of the complexes in solutions, along with quantum-chemical calculations, reveals that the spin density is predominantly localized at their metal centers. The superposition of trajectory maps of the electron density gradient vector field ∇ ρ r ${\nabla \rho \left({\bf r}\right)}$ and the electrostatic force density field F e s r ${{{\bf F}}_{{\rm e}{\rm s}}\left({\bf r}\right)}$ per electron, as well as the atomic charges, discloses that, within the first coordination sphere, the interatomic charge transfer occurs from the metal atom to the ligand atoms and that the complex anions can thus be formally described by the general formulae (dpp-bian)2-Ni+(COD) and (dpp-bian)2 -Ni+. It was also shown that the reduced nickel complexes can be oxidized by formic acid; resulting from this reaction, the two-electron and two-proton addition product dpp-bian-2H is formed.

Cobalt(II) coordination to an N4-acenaphthene-based ligand and its sodium complex.

A new bifunctional N4-ligand was obtained via the condensation reaction of acenaphthenequinone and 2-picolylamine. A peculiarity of this synthesis is the formation of a new intramolecular C-C bond during the reaction. The structure and redox properties of the ligand were studied. The anion-radical form of the ligand was prepared via the chemical reduction of the latter with metallic sodium as well as in situ via its electrochemical reduction in a solution. The sodium salt prepared was structurally characterized using single-crystal X-ray diffraction (XRD). New cobalt complexes with the ligand in neutral and anion-radical forms were synthesized and further studied. As a result, three new homo- and heteroleptic cobalt(II) complexes were obtained, in which the cobalt atom demonstrates different modes of coordination with the ligand. Cobalt(II) complex CoL2 with two monoanionic ligands was prepared by the electrochemical reduction of a related L2CoBr2 complex or by treating cobalt(II) bromide with the sodium salt. XRD was used to study the structures of all cobalt complexes prepared. Magnetic and electron paramagnetic resonance studies were performed: CoII ion states with S = 3/2 and S = 1/2 were found for the complexes. A quantum-chemical study confirmed that the spin density is mainly located at the cobalt center.

One-Electron Reduction of Acenaphthene-1,2-Diimine Nickel(II) Complexes.

New nickel-based complexes of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian) with BF4 - counterion or halide co-ligands were synthesized in THF and MeCN. The nickel(I) complexes were obtained by using two approaches: 1) electrochemical reduction of the corresponding nickel(II) precursors; and 2) a chemical comproportionation reaction. The structural features and redox properties of these complexes were investigated by using single-crystal X-ray diffraction (XRD), cyclic voltammetry (CV), and electron paramagnetic resonance (EPR) and UV/Vis spectroscopy. The influence of temperature and solvent on the structure of the nickel(I) complexes was studied in detail, and an uncommon reversible solvent-induced monomer/dimer transformation was observed. In the case of the fluoride complex, the unpaired electron was found to be localized on the dpp-bian ligand, whereas all of the other nickel complexes contained neutral dpp-bian moieties.

Synthesis, structure and biological activity of nitroxide malonate methanofullerenes.

Two nitroxide methanofullerenes was synthesized for the first time, and their structures and biological activities studied. It was shown by X-ray single crystal analysis that the methanofullerene with two nitroxide groups forms a 1 : 2 inclusion complex with chloroform and has a nearly tetrahedral (diamond-like) arrangement of fullerene-fullerene interactions in the crystal. For the first time, it has been found that malonate nitroxide methanofullerene in combination with the known anticancer drug cyclophosphamide (CPA) shows high antitumor activity against leukemia P-388.

The effects of high-intensity exercise on skeletal muscle neutrophil myeloperoxidase in untrained and trained rats.

The primary purpose of this study was to examine the effects of high-intensity acute exercise on neutrophil infiltration in different muscle fiber types of untrained rats and to compare postexercise neutrophil accumulation in muscles of untrained and trained animals. The effect of high-intensity acute exercise on blood neutrophil degranulation reaction in trained animals was also elucidated. Neutrophil enzyme myeloperoxidase (MPO) was determined as a measure of neutrophil migration into muscles and blood neutrophil degranulation. Male albino rats were subjected to acute exercise and 5 weeks of training. The used model of intensive acute exercise consisted of 5, 15, and 25 intermittent swimming bouts with the addition of weight (8% of total body mass) for 1-min each, followed by 1.5-min rest intervals. MPO was analyzed in quadriceps muscle (white and red portion) and in soleus muscle 24 h after acute exercise. MPO content in resting blood plasma and neutrophils was determined 48-h following the completion of a training process. In addition, MPO content in the trained rats was measured immediately (in blood plasma and neutrophils) after and 24 h (in muscles) following a single-bout of exercise to exhaustion. The remaining two-third of the trained animals were exposed to a single-bout of nonstop swimming with the addition of 6% body mass until exhaustion. These animals were sacrificed immediately and 24 h after loaded swimming to analyze leukocyte count, MPO content in blood plasma and neutrophils and in muscles, respectively. About 24 h after exercise MPO concentrations in the red portion of quadriceps muscle and in soleus muscle were 4-7-fold higher as compared to the white portion of m. quadriceps. There was an association between the quantity of repetitive bouts of swimming and MPO content in the muscles. The duration of swimming to exhaustion of trained rats was 3.8-fold longer than untrained sedentary control. At rest, plasma MPO concentration was found to be 40% higher in trained rats compared to untrained controls (P < 0.05). Postexercise plasma MPO concentrations were significantly higher both in untrained (+137%; P < 0.05) and trained (+81%; P < 0.05) rats compared to resting values. At rest neutrophil MPO concentration was found to be 33% lower in trained rats compared to untrained controls (P < 0.05). There were no significant differences in muscle MPO concentrations between untrained and trained rats at rest. A single-bout of exercise to exhaustion produced a greater increase in MPO content in untrained compared to trained rats. The data suggest that postexercise neutrophil infiltration is more intensive in red fibers types compared to white fiber types. A smaller neutrophil infiltration in muscles of trained animals after exhaustive exercise suggests a protective effect of previous training to muscle injury.

Effect of exercise to exhaustion on myeloperoxidase and lysozyme release from blood neutrophils.

Exercise sessions (swimming in rats and treadmill running in humans) resulted in stimulation of neutrophil degranulation in the experiments with animals and in the human study. Myeloperoxidase (MPO) (+67%) and lysozyme (+51%) quantities in the plasma of rats increased significantly immediately after exercise. The blood plasma lysozyme concentration was increased by 41% at the 6th min of treadmill exercise in athletes. The blood concentrations of neutrophil proteins normalized both in humans and animals at rest. The neutrophil protein concentrations in blood increased in parallel with the decrease of their level in leukocytes. The neutrophil capacity for an oxidative burst was not changed by the exercise, but decreased for 3-6 h in the post-exercise period. Such dynamics of the oxidative burst activity suggest a lack of association between this parameter and the degranulation process. The neutrophil proteins that appear in blood during degranulation can be involved in enhancing the bactericidal potency of blood, the activation of granulopoiesis, neutrophil efflux from bone marrow, and the conditioning of blood endothelium for leukocyte extravasation.