Nanosized cationic and anionic manganese porphyrins as mesoporous catalysts for the oxidation of olefins: Nano versus bulk aggregates

In this study, catalytic activity of bulk and nano‐sized meso‐tetrakis(4‐sulfonatophenyl)porphyrinatomanganese(III) acetate, MnTPPS₄(OAc), (ammonium salt) and meso‐tetrakis(3‐methylpyridyl)porphyrinatomanganese(III) acetate, MnT(3‐MePy)P(OAc) (tosylate salt) for the oxidation of olefins with tetra‐n‐butylammonium Oxone has been studied and compared with that of the bulk counterparts. The nanoparticles were prepared by mixing solvent techniques using water, (triethyleneglycol) monomethyl ether and dimethylsulfoxide or acetonitrile. The formation of nano‐sized catalysts was confirmed by UV‐Vis spectroscopy, DLS and AFM. Nitrogen porosimetry measurements indicated the homogeneous pore size distribution in the bulk and nano‐sized manganese porphyrins. In spite of the high oxidizability of Oxone, the heterogenized manganese porphyrins showed a significantly higher oxidative stability relative to their homogeneous counterparts within a reaction time of 6 h. The increase in the catalytic activity induced by the formation of nano‐sized catalysts was more pronounced in the case of MnT(3‐MePy)P(OAc). MnT(3‐MePy)P(OAc) may be recovered and reused for at least 4 times without any significant decrease in the catalyst efficiency. In the case of MnTPPS₄(OAc) a large decrease in the catalytic activity was observed after the first use of the catalyst. The latter was attributed to higher degrees of catalyst degradation in the case of MnTPPS₄(OAc).     

Synthesis,spectral, DFT calculations and antibacterial studies of Fe(III) complexes of new fluorescent Schiff bases derived from imidazo[4',5':3,4]benzo[1,2‐c]isoxazole

New fluorescent heterocyclic ligands were synthesized by the reaction of 8‐(4‐chlorophenyl)‐3‐alkyl‐3H‐imidazo[4',5':3,4]benzo [1,2‐c]isoxazol‐5‐amine with p‐hydroxybenzaldehyde and p‐chlorobenzaldehyde in good yields. The coordination ability of the ligands with Fe³⁺ ion was examined in an aqueous metanolic solution. Schiff base ligands and their metal complexes were characterized by elemental analyses, IR, UV–vis, mass, and NMR spectra. The optical properties of the compounds were investigated and the results showed that the fluorescence of all compounds is intense and their obtained emission quantum yields are around 0.15 – 0.53. Optimized geometries and assignment of the IR bands and NMR chemical shifts of the new complexes were also computed by using density functional theory (DFT) methods. The DFT‐calculated vibrational wavenumbers and NMR chemical shifts are in good agreement with the experimental values, confirming suitability of the optimized geometries for Fe(III) complexes. Also, the 3D‐distribution map for HOMO and LUMO of the compounds were obtained. The new compounds showed potent antibacterial activity and their antibacterial activity (MIC) against Gram‐positive and Gram‐negative bacterial species were also determined. Results of antibacterial test revealed that coordination of ligands to Fe(III) leads to improvement in the antibacterial activity.     

Synthesis,structure and catalytic polymerization activity of half‐sandwich cyclometallated iridium complexes

A series of mononuclear half‐sandwich cyclometallated iridium complexes with Schiff base ligands were synthesized in good yields. Five air‐stable C,N‐chelate mode complexes were obtained smoothly through metal‐mediated C─H bond activation. Treatments of dimeric metal complexes [Cp*IrCl₂]₂ with ligands L1–L5 afforded the corresponding C,N‐chelate mononuclear half‐sandwich iridium(III) complexes 1 – 5 . These iridium complexes exhibit high catalytic activity for norbornene polymerization. Both steric and electronic effects of the substituted groups have influences on the behaviors of the polymerization process. All complexes were characterized using infrared and NMR spectroscopies and elemental analysis. Molecular structures of complexes 1 , 2 and 5 were further confirmed using single‐crystal X‐ray analysis.     

席夫碱类三明治型铽/镝金属配合物的合成、表征及磁性

以N,N′-二(4-甲氧基水杨基)邻苯二胺(H2L)为配体合成了2个新的稀土配合物[M_2L_3(H_2O)](M=Tb (1),Dy (2)),并对它们进行了红外分析、元素分析和单晶结构分析。单晶衍射结果表明,配合物1和2均为三明治型双核配合物。此外还研究了配合物1和2的磁学性质,结果表明配合物1和2都表现出反铁磁性作用和场诱导效应引起的慢弛豫行为。配合物2的有效能垒和驰豫时间分别为35.45 cm-1和2.7×10~(-10) s。     

Kinetics and mechanistic aspects on electron‐transfer process for permanganate oxidation of poly(ethylene glycol) in aqueous acidic solutions in the presence and absence of Ru(III) catalyst

The kinetics and mechanism of oxidation of poly(ethylene glycol) (PEG) by the permanganate ion as a multiequivalent oxidant in aqueous perchlorate solutions at an ionic strength of 2.0 mol dm⁻³ has been investigated spectrophotometrically. The reaction kinetics was found to be of complex in nature. The pseudo–first‐order plots showed curves of inverted S‐shape, consisting of two distinct stages throughout the entire course of reaction. The first stage was relatively slow, followed by a fast reaction rate at longer time periods. The first‐order dependence in [MnO₄⁻], fractional first‐order dependence in [H⁺], and fractional first‐order kinetics in the PEG concentration for the first stage have been revealed in the absence of the Ru(III) catalyst. The influence of the Ru(III) catalyst on the oxidation kinetics has been examined. The oxidation was found to be catalyzed by the added Ru(III) catalyst. The First‐order dependence on the catalyst and zero order with respect to the oxidant concentrations have been observed. The kinetic parameters have been evaluated, and a tentative reaction mechanism consistent with the kinetic results is suggested and discussed.     

Ru(III), Cr(III), Fe(III) complexes of Schiff base ligands bearing phenoxy Groups: Application as catalysts in the synthesis of vitamin K3

Two polydentade Schiff base ligands and their Ru(III), Cr(III) and Fe(III) complexes were synthesized and characterized by elemental analysis (C, H, N), UV/Vis, FT IR, ¹H and ¹³C NMR, LC–MS/MS, molar conductivity and magnetic susceptibility techniques. The absorption bands in the electronic spectra and magnetic moment measurements verified an octahedral environment around the metal ions in the complexes. The thermal stabilities were investigated using TGA. The synthesized complexes were used in the catalytic oxidation of 2-methyl naphthalene (2MN) to 2-methyl-1,4-naphthoquinone; vitamin K₃, menadione, 2MNQ; using hydrogen peroxide, acetic acid and sulfuric acid. L₁-Fe(III) complex showed very efficient catalytic activity with 58.54% selectivity in the conversions of 79.11%.     

Gold catalysed Suzuki-Miyaura coupling of arenediazonium o-benzenedisulfonimides

Arenediazonium o-benzenedisulfonimides have been used as efficient electrophilic partners in Au(I) catalysed Suzuki coupling reactions. The synthetic protocol is general, easy and produced either biaryls or heteroaryl arenes in good yields (51 positive examples, average yield 80%). o-Benzenedisulfonimide was recovered at the end of the reactions and was reused to prepare the starting salts for further reactions. Mechanistic insights suggest that the o-benzenedisulfonimide anion act as an electron transfer agent and promotes a catalytic cycle which does not require the presence of photocatalysts or external oxidants.     

Anilinopyridine–metal complexes for the selective chromogenic sensing of cyanide anion

Abstract

Probe 1, which contains an anilinopyridine chromophore and an aza-oxa macrocyclic subunit, presented an absorption band centered at 340 nm in acetonitrile. Addition of Fe(III), Cr(III) and Hg(II) induced the growth of a new absorption band at 430 nm (with color change from colorless to yellow), whereas in the presence of Cu(II), Zn(II) and Pb(II), less marked changes were observed. The color changes observed upon addition of Fe(III), Cr(III) and Hg(II) were ascribed to the formation of 1:1 stoichiometry complexes with probe 1. Coordination of Fe(III), Cr(III) and Hg(II) with the pyridine fragment of 1 induced an enhancement of the charge transfer character accompanied with a marked bathochromic shift that was reflected in a color change from colorless to yellow. The strength of the interaction between probe 1 and Fe(III) cation was modulated upon interaction with anions. Of all the anions tested, only cyanide was able to induce the bleaching of the yellow 1·Fe(III) complex solution. This bleaching was ascribed to the formation of 1·Fe(III)-CN complex that restored, to some extent, the optical features of the free probe allowing the chromogenic sensing of cyanide. Besides, 1·Fe(III) complex was used to detect cyanide in acetonitrile-water 90:10 v/v mixtures with good recoveries.     

Reactions of carbonate radical anion with amino-carboxylate complexes of manganese(II) and iron(III)

Abstract

The reaction kinetics of eight amino-carboxylate complexes of Fe(III) and Mn(II) with carbonate radical anion were studied using the pulse radiolysis method and UV-vis spectroscopy. Difference spectra revealed the formation of Fe(IV) and Mn(III) after reaction with CO₃^??. Spectral measurements revealed the first step to be the coordination of carbonate to the metal center. All of these led to the conclusion that the role of coordinated carbonate is essential to the electron transfer process by carbonate radical anion.     

Nicotinamide complex of silver(III) with expanded coordination number

Abstract

In strongly alkaline media ([OH^?]?≥?0.12 M), nicotinamide (nica) forms a complex with square-planar Ag(OH)₄^? [nica]?≥?0.05 M. The complex decomposes in seconds to nicotinamide N-oxide. The correlation of maximum absorbance of the complex with concentrations of nicotinamide and hydroxide requires that the complex is either the five-coordinate Ag(OH)₄(H_-1nica)^2? or the six-coordinate Ag(OH)₅(nica)^2?. Comparison with the reactions of Ag(OH)₄^? with nicotinate ion (nic^?) and acetamide under similar conditions indicates that nicotinamide coordinates with Ag(OH)₄^? by the amido group rather than the nitrogen on the pyridine ring or the amido oxygen. Kinetics of the Ag(III)-nica redox reaction are consistent with direct reaction between nicotinamide and uncoordinated Ag(OH₄)^?. Oxidation takes place at the pyridine ring, yielding nicotinamide N-oxide. Silver(III) is reduced to monovalent silver.