Direct synthesis of hyperbranched ethene oligomers and ethene-MA co-oligomers using iminopyridyl systems with weak neighboring group interactions

The synthesis of hyper-branched ethene oligomers through catalytic insertion reactions with late transition metal catalysts is unique in its synthetic and practical scope. In this study, a series of iminopyridyl Ni(II) and Pd(II) complexes with electron-rich distal aryl motifs were synthesized and characterized. These complexes were very efficient in ethene oligomerization and co-oligomerization with methyl acrylate (MA). Hyperbranched ethene oligomers with different microstructures were generated using different metal species in ethene oligomerization. More importantly, hyperbranched ethene-MA co-oligomers with varying incorporation ratios were generated via ethene and MA co-oligomerization using the Pd(II) complexes. Most notably, weak neighboring group interactions of distal aryl motifs in the nickel system are more effective in influencing the microstructure of ethene oligomers than the corresponding palladium system.     

Structure of Zinc and Nickel Histidine Complexes in Solution Revealed by Molecular Dynamics and Raman Optical Activity

The histidine residue has an exceptional affinity for metals, but solution structure of its complexes are difficult to study. For zinc and nickel complexes, Raman and Raman optical activity (ROA) spectroscopy methods to investigate the link between spectral shapes and the geometry were used. The spectra were recorded and interpreted on the basis of ionic equilibria, molecular dynamics, ab initio molecular dynamics, and density functional theory. For zwitterionic histidine the dominant tautomer was determined by the decomposition of experimental spectra into calculated subspectra. An octahedral structure was found to prevail for the ZnHis₂ complex in solution, in contrast to a tetrahedral arrangement in the crystal phase. The solution geometry of NiHis₂ is more similar to the octahedral structure found by X-ray. The Raman and ROA structural determinations of metal complexes are dependent on extensive computations, but reveal unique information about the studied systems.     

Synthesis,structure and catalytic properties of Pdii-based bimetallic complexes with ferrocenecarboxylic acid

Novel highly soluble palladium-based complexes with ferrocenecarboxylic acid of general formula [Pd(lut)₂(FcCOO)₂] (lut is 2,6-or 3,4-lutidines) were synthesized and structurally characterized by single-crystal X-ray diffraction. The catalytic oxidation of 1,2-diphenyl-acetylene with these complexes gave dibenzo[a,e]pentalene derivative along with other products.     

New azo derivative and their divalent metal ion complexes: Synthesis,characterization, and evaluation of their antibacterial activity

A new azo derivative 3-((4-H1benzo[d]imidazole-2-yl)-4-hydroxy benzaldehyde was prepared by reaction of benzimidazole derivative with 4-hydroxy benzaldehyde. The all-final compounds were diagnosis and determined the structure of these compounds using a variety of spectroscopic methods, including 1H-NMR, FT-IR, UV-Vis, mass spectrometry magnetic susceptibility and atomic absorption spectroscopy. The results showed that all metal ion complexes have an octahedral shape. Antimicrobial activity of the ligand and its metal ion complex had been tested against some selected microorganism such Streptococcus pyogenes a species of Gram-positive and Pseudomonas aeruginosa is a common bacterium gram-negative, all prepared compounds displayed a strong antibacterial activity. Taken together, the results of the current study indicated that the new Azo derivative and their divalent metal ion complexes could be used as a future strategy for other biomedical applications.     

The unusual stability of H-bonded complexes in solvent caused by greater solvation energy of complex compared to those of isolated fragments

Here, the effect of solvent on the stability of non-covalent complexes, was studied. These complexes were from previously published S22, S66, and X40 datasets, which include hydrogen-, halogen- and dispersion-bonded complexes. It was shown that the charge transfer in the complex determines whether the complex is stabilized or destabilized in solvent.     

三核过渡金属配合物在催化反应中的研究进展

多核过渡金属配合物作为一类广泛应用的均相催化剂,其设计灵感往往来自天然酶的多金属活性位点所发挥的重要作用.目前,三核金属配合物作为活化小分子的多金属催化剂受到了广泛的关注.为深入理解三核过渡金属配合物在催化反应中作用特点,对近年报道的代表性三核过渡金属配合物按金属中心进行分类,并对配体环境形成特点及催化应用进行综述.从金属中心出发,讨论了三核过渡金属配合物的几何结构和电子特征;从配体环境出发,总结了关联三个独立的金属位点的配位环境特征;在催化应用方面,重点综述了三核过渡金属配合物在涉及特定化学键活化反应的催化作用机制,最后对三核过渡金属配合物的催化应用前景进行展望.     

Synthesis and cytotoxicity studies of new 1,2,4-thiadiazole derivatives and their zinc complexes

A new polyfunctional ligand of the thiadiazole family was synthesized. Cytotoxic properties with respect to leukemic cell lines, radiation stability, predicted permeability through the blood–brain barrier and cardiotoxicity of the new ligand and its precursor were determined. New zinc complexes with N-{2-[5-(3-chloro-4-methylphenylamino)-1,2,4-thiadiazol-3-yl]-1-methylethyl}-N-(2,2,6,6-tetramethylpiperidin-4-yl)-amine as the ligand have been obtained.     

A pyridine promoted ‘weak base route’ to (NHC)2NiCl2 complexes with bulky N,N'-diaryl carbene ligands

A simple one-step synthesis of (NHC)₂NiCl₂ complexes containing bulky N-heterocyclic carbene (NHC) ligands relies on the C–H metallation of N,N'-diaryl-substituted azolium salts, NHC-precursors, with NiCl₂Py₂ in the presence of Cs₂CO₃ and pyridine. This procedure allows one to implement all synthetic manipulations in air.     

Manipulating Host-Guest Charge Transfer of a Water-Soluble Double-Cavity Cyclophane for NIR-II Photothermal Therapy

Water-soluble small organic photothermal agents (PTAs) over NIR-II biowindow (1000–1350 nm) are highly desirable, but the rarity greatly limits their applications. Based on a water-soluble double-cavity cyclophane GBox-4⁴⁺ , we report a class of host–guest charge transfer (CT) complexes as structurally uniform PTAs for NIR-II photothermal therapy. As a result of its high electron-deficiency, GBox-4⁴⁺ can bind different electron-rich planar guests with a 1 : 2 host/guest stoichiometry to readily tune the CT absorption band that extends to the NIR-II region. When using a diaminofluorene guest substituted with an oligoethylene glycol chain, the host–guest system realized both good biocompatibility and enhanced photothermal conversion at 1064 nm, and was then exploited as a high-efficiency NIR-II PTA for cancer cell and bacterial ablation. This work broadens the potential applications of host–guest cyclophane systems and provides a new access to bio-friendly NIR-II photoabsorbers with well-defined structures.     

Assembled Porphyrin-Based Multinuclear Ruthenium(II)-NNNN Complex Catalysts for Transfer Hydrogenation of Ketones

Multinuclear porphyrin-based ruthenium(II)-NNNN complexes were efficiently assembled by means of coordinatively unsaturated 16-electron mononuclear ruthenium(II)-pyrazolyl-imidazolyl-pyridine complex, zinc(II) meso-tetra(4-pyridyl)-porphyrin (ZnTPyP), and 4,4′-linked bipyridines. The resultant multinuclear (Ru₄ and Ru₈) porphyrin-based ruthenium(II)-NNNN complexes exhibited exceptionally high catalytic activity at as low as 0.008 mol % Ru loading for the transfer hydrogenation reaction of ketones in refluxing 2-propanol, reaching up to 99 % yields and 5.7×10⁶ h⁻¹ TOFs.