Influence of the Substituent's Size in the Phosphinate Group on the Conformational Possibilities of Ferrocenylbisphosphinic Acids in the Design of Coordination Polymers and Metal-Organic Frameworks.

This paper illustrates how the size and type of substituent in the phosphinate group of ferrocenyl bisphosphinic acids can affect conformational possibilities and coordination packing. It also demonstrates that -phosphinate plays a key role in variational mobility, while Me- or Ph- substituents of the phosphinate group can only lead to 0D complexes or 1D coordination polymer. Overall, this paper provides valuable insights into the design and construction of coordination polymers based on ferrocene-contained linkers.

The Phosphinate Group in the Formation of 2D Coordination Polymer with Sm(III) Nodes: X-ray Structural, Electrochemical and Mössbauer Study.

A coordination polymer has been synthesized using ferrocene-based ligand-bearing phosphinic groups of 1,1'-ferrocene-diyl-bis(-phosphinic acid)), and samarium (III). The coordination polymer's structure was studied by both single-crystal and powder XRD, TG, IR, and Raman analyses. For the first time, the Mössbauer effect studies were performed on ferrocenyl phosphinate and the polymer based on it.

Synthesis, antitumor activity and structure-activity studies of novel pyridoxine-based bioisosteric analogs of estradiol.

A new efficient approach to the synthesis of 6-alkenyl substituted pyridoxine derivatives has been developed. A series of 31 novel alkenyl pyridoxine derivatives, stilbene-based bioisosteric analogs of estradiol, were synthesized. In vitro cytotoxicity of the obtained compounds against MCF-7 (ER+) breast cancer tumor cells was studied using the MTT assay.

Sterically Hindered Phosphonium Salts: Structure, Properties and Palladium Nanoparticle Stabilization.

A new family of sterically hindered alkyl(tri--butyl) phosphonium salts (-CH with = 2, 4, 6, 8, 10, 12, 14, 16, 18, 20) was synthesized and evaluated as stabilizers for the formation of palladium nanoparticles (PdNPs), and the prepared PdNPs, stabilized by a series of phosphonium salts, were applied as catalysts of the Suzuki cross-coupling reaction. All investigated phosphonium salts were found to be excellent stabilizers of metal nanoparticles of small catalytically active size with a narrow size distribution. In addition, palladium nanoparticles exhibited exceptional stability: the presence of phosphonium salts prevented agglomeration and precipitation during the catalytic reaction.

Synthesis, structure, and electrochemical properties of 4,5-diaryl-1,2,3-triphosphaferrocenes and the first example of multi(phosphaferrocene).

The reaction between aryl substituted sodium 1,2,3-triphospholides or disodium bis(1,2,3-triphospholide) and [Fe(η6-(C6H5CH3)Cp]+[PF6]- in boiling diglyme results in pure 1,2,3-triphosphaferrocenes 1-3 or bis(1,2,3-triphosphaferrocene) 4, respectively, in good yields. The structure of all obtained 1,2,3-triphosphaferrocenes 1-4 has been extensively studied experimentally (NMR, UV-Vis spectroscopy, and X-ray analysis for 1 and 4) and quantum chemically. The electrochemical properties of 1,2,3-triphosphaferrocenes 1-4 in the solid state were studied for the first time and a reversible one-electron oxidation (E1/2 = 0.

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 BF 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.

Synthesis and in vitro antitumor activity of novel alkenyl derivatives of pyridoxine, bioisosteric analogs of feruloyl methane.

Two series of novel pyridoxine-based azaheterocyclic analogs of feruloyl methane (Dehydrozingerone, DZG) were synthesized, and their biological activity against a panel of tumor and normal cell lines was evaluated in vitro. The most active compounds possessed expressed cytotoxic activity, which was comparable to cytotoxic activity of doxorubicin and significantly higher than that of DZG, and a remarkable selectivity for the studied cancer cell lines as compared to the normal cells. The leading compound and DZG initiated arrest of the cell cycle in the G2/M phase, preventing normal division and further transition of daughter cells to the G0/G1 phase.

Calixarene alpha-ketoacetylenes: versatile platforms for reaction with hydrazine nucleophile.

Late stage diversification of calix[4]arenes and thiacalix[4]arenes with heterocycles remains a significant synthetic challenge and hampers further exploitation of the scaffolds. Here we describe the development of a short and facile synthetic route to conformationally diverse novel calix[4]arene and thiacalix[4]arene ynones using a palladium cross coupling approach (5% Pd(ii) + 10% Cu(i)) with benzoyl chloride. Their successful conversion to heterocycles to afford pyrazoles was demonstrated through treatment with hydrazine.

Structure of copper(II) complexes grown from ionic liquids - 1-ethyl-3-methyl-imidazolium acetate or chloride.

Crystals of four new copper(II) complexes have been grown from copper(II) acetate/chloride-1-ethyl-3-methyl-imidazolium acetate/chloride-water systems and characterized by X-ray analysis. The first complex, bis-(1-ethyl-3-methyl-imidazolium) tetra-μ-acetato-bis[chloridocuprate(II)], [Emim][Cu(CHO)Cl] () (Emim is 1-ethyl-3-methyl-imidazolium, CHN), contains [Cu(CHO)Cl] coordination anions with a paddle-wheel structure and ionic liquid cations. Two of the synthesized complexes are one-dimensional polymers, namely -poly[1-ethyl-3-methyl-imidazolium [[tetra-μ-acetato-dicuprate(II)]-μ-chlorido] monohydrate], {[Emim][Cu(CHO)Cl]·HO} (), and -poly[1-ethyl-3-methyl-imidazolium [[tetra-μ-acetato-dicuprate(II)]-μ-acetato]], {[Emim][Cu(CHO)]} ().

A new surfactant-copper(ii) complex based on 1,4-diazabicyclo[2.2.2]octane amphiphile. Crystal structure determination, self-assembly and functional activity.

A new surfactant-copper(ii) complex [Cu(L)Br3] (where LBr is 1-cetyl-4-aza-1-azoniabicyclo[2.2.2]octane bromide) containing a transition metal in the head group has been synthesized and characterized.

The isomeric structure of pentacoordinate chiral spirophosphoranes in solution by the combined use of NMR experiments and GIAO DFT calculations of NMR parameters.

The interplay of NMR experiments and DFT calculations of NMR parameters is a reliable method for determining the relative configurations of pentacoordinate chiral spirophosphoranes bearing two six- or five-membered rings at the phosphorus atom in solution. The major product of the Betti based derivatives corresponds to the isomers with both substituents at chiral carbons being opposite to the P-H proton. The next populated product corresponds to the isomer with different chiralities at carbons.

Redox trends in cyclometalated palladium(ii) complexes.

A series of diverse binuclear and mononuclear cyclometalated palladium(ii) complexes of different structure was investigated by electrochemical techniques combined with density functional theory (DFT) calculations. The studies including cyclic and differential pulse voltammetry, X-ray structure analysis and quantum chemical calculations revealed a regularity of the complexes oxidation potential on the metal-metal distance in the complexes: the larger Pd-Pd distance, the higher oxidation potentials. The reduction potentials feature unusually high negative values while no correlation depending on the structure could be observed.

Synthesis and magnetic properties of manganese carbonyl complexes with different coordination modes of 3,4,5-triaryl-1,2-diphospholide ligands.

The set of complexes bis-(μ:η(1),η(1)-3,4,5-triaryl-1,2-diphosphacyclopentadienyl)-bis-(tetracarbonyl manganese(i)) (aryl = C6H5 (), p-FC6H4 (), p-ClC6H4 ()) undergo an irreversible rearrangement to mononuclear 3,4,5-triaryl-1,2-diphosphacymantrenes (). According to quantum-chemical calculations binuclear complexes can be considered to be products of kinetic control and mononuclear species are thermodynamically favorable compounds. The antiferromagnetic intramolecular interaction observed for complexes can be effectively tuned by using substituents in the para-position of the arene ring, whereas mononuclear 1,2-diphosphacymantrenes are diamagnetic.

The C-H bond activation in 1-ethyl-3-methylimidazolium acetate-copper(II) acetate-water-air (dioxygen) systems.

Ionic liquid (1-ethyl-3-methylimidazolium acetate, [C2C1im][AcO])-copper(ii) diacetate monohydrate-water-air (O2) systems have been investigated by (13)C NMR, EPR, spectrophotometry, HPLC, and synthetic chemistry methods at different temperatures. The C-H bond activation of [C2C1im](+) with the formation of the unusual dication 1,1'-diethyl-3,3'-dimethyl-2,2'-biimidazolium ([(C2C1im)2](2+)) at 50 °C and 1-ethyl-3-methyl-1H-imidazol-2(3H)-one (C2C1imO) at 50-85 °C was revealed. Two new complexes with the above compounds, [(C2C1im)2][Cu(AcO)4] and Cu2(AcO)4(C2C1imO)2, were isolated from the systems and characterized by X-ray structural analysis.

Self-assembling systems based on amphiphilic alkyltriphenylphosphonium bromides: elucidation of the role of head group.

A systematic study of the aggregation behavior of alkyltriphenylphosphonium bromides (TPPB-n; n=8, 10, 12, 14, 16, 18; here n is the number of carbon atoms in alkyl groups) in aqueous solutions has been carried out and compared with trimethyl ammonium bromides (TMAB-n). Critical micelle concentrations (cmcs) of TPPB-n and TMAB-n decrease with the number of carbon atoms with the slope parameter of ca.0.

Self-assembly of neutral hexanuclear circular copper(II) meso-helicates: topological control by sulfate ions.

Bis-pyridylimine ligands with different linking elements are capable of forming unique hexanuclear circular Cu(II) meso-helicates; the self-assembly is controlled by coordination of sulfate ions to the metal centres.

1-(Alpha-aminobenzyl)-2-naphthol: a new chiral auxiliary for the synthesis of enantiopure alpha-aminophosphonic acids.

A new diastereoselective synthesis of alpha-aminophosphonates has been developed, based on the reaction, in the presence of trifluoroacetic acid, of trialkyl phosphites with chiral imines derived from (R)- or (S)-1-(alpha-aminobenzyl)-2-naphthol. The reaction proceeds at room temperature in toluene with high diastereoselectivity. The major diastereomer can be separated by crystallization from an appropriate solvent.