New Group 6 metal carbonyl derivatives of 2-(2'(-pyridyl)benzimidazole: synthesis and spectroscopic studies

Reaction of Cr(CO)(6) with 2-(2'-pyridyl)benzimidazole (pbiH) under reduced pressure resulted in the formation of the dinuclear complex [Cr(2)(CO)(6)(pbiH)(2)]. Infra-red (IR) spectroscopy revealed the presence of terminal and bridge Cr-CO bonds. Interaction of M(CO)(6), M=Cr, Mo and W, with pbiH in the presence of 2,2'-bipyridine (bpy) gave the tetracarbonyl complexes [M(CO)(4)(pbiH)].bpy. Spectroscopic studies of the complexes indicated the presence of hydrogen bonding between the bpy nitrogen and the NH group of pbiH. Reactions of M(CO)(6) with pbiH in the presence of PPh(3) gave the tricarbonyl monosubstituted derivatives [M(CO)(3)(PPh(3))(pbiH)]. The spectroscopic studies of the complexes suggested the proposed structures.     

Reaction of some coumarin and 4,6-diaryl-2H-pyran derivatives with secondary amines

The reaction of piperidine, morpholine, piperazine or dimethylamine with several coumarins, 3-bromocoumarin, 4,6-diaryl-2H-pyran-2-ones and 3-bromo-4,6-diaryl-2H-thiopyran-2-ones gave o-hydroxycinnamic acid amides, benzofurans, open-chain δ-oxoamides and thiophene derivatives, respectively.     

Selective adsorption from methanol/water mixtures by C60 fullerene nanospheres

Micro-Raman spectroscopy was used to investigate the selective adsorption of methanol/water mixtures on the surface of [60] fullerene nanospheres. C₆₀ molecules were dispersed in methanol/water mixtures with different methanol molar fractions ranging between 1 and 0.5. The Raman active pentagon pinch mode shifted significantly (±4 cm⁻¹) as the mixture composition was changed. The shift in the Raman mode was sinusoidal in nature indicating that methanol then water is adsorbed preferentially on the fullerene surface at different mixture compositions. The observed behavior is attributed to structure forming effects of alcohol/water mixtures and the shape and size effect of fullerene surface.     

Diammonium Hydrogen Phosphate as an Efficient and Inexpensive Catalyst for the Synthesis of Bis(indolyl)methanes under Solvent-Free Conditions

Bis(indolyl)methanes were synthesized by the reaction of indole derivatives and aromatic and aliphatic aldehydes in the presence of diammonium hydrogen phosphate as a solid catalyst under solvent-free conditions. This methodology offers significant improvements for the synthesis of bis(indolyl)methanes with regard to the yield of products, simplicity in operation, and green aspects by avoiding toxic catalysts and solvents.     

Theoretical study on interaction of different coordination modes of BH4 ligand with transition metal in [TM(BH4)(CO)4] (TM = Cr, Mo)

Density functional calculations were performed on bonding and structural features of [(ηⁿ-BH₄)TM(CO)₄]⁻ (n = 1, 2, 3; TM = Cr, Mo) complexes. Calculations show that the ground state is bidentate which is in good agreement with experimental results. It has been found that the bridge and terminal hydrogen atoms will interchange by two pathways: (i) twist of BH₄ about one of the bridge B-H and (ii) twist of BH₄ about one of the terminal B-H. The molecular orbital calculations and natural bond orbital methodologies for different isomers of these complexes have been evaluated. The final results indicate that case (i) is more preferable relative to another case.     

Stability-indicating methods for determination of pyritinol dihydrochloride in the presence of its precursor and degradation product by derivative spectrophotometry

A first-derivative spectrophotometric (1D) method and a derivative-ratio zero-crossing spectrophotometric (1DD) method were used to determine pyritinol dihydrochloride (I) in the presence of its precursor (II) and its degradation product (III) with 0.1N hydrochloric acid as a solvent. Linear relationships were obtained in the ranges of 6-22 microg/mL for the (1D) method and 6-20 microg/mL for the (1DD) method. By applying the proposed methods, it was possible to determine pyritinol dihydrochloride in its pure powdered form with an accuracy of 100.36 +/- 1.497% (n = 9) for the (1D) method and an accuracy of 99.92 +/- 1.172% (n = 8) for the (1DD) method. Laboratory-prepared mixtures containing different ratios of (I), (II), and (III) were analyzed, and the proposed methods were valid for concentrations of < or = 10% (II) and < or = 50% (III). The proposed methods were validated and found to be suitable as stability-indicating assay methods for pyritinol in pharmaceutical formulations.     

A new approach to the facile synthesis of mono- and disubstituted quinazolin-4(3H)-ones under solvent-free conditions

Quinazolin-4(3H)-one derivatives were synthesized successfully via a one-pot, three component reaction of isatoic anhydride and an orthoester with ammonium acetate or a primary amine catalyzed by silica sulfuric acid under solvent-free conditions. This is the first report on the synthesis of 2-substituted quinazolin-4(3H)-ones by this procedure.     

Characterization of the new Bi∼6.2Cu∼6.2O8(PO4)5 oxyphosphate; a disordered compound containing 2- and 3-O(Bi, Cu)4 tetrahedra—wide polycationic ribbons

The present work is dedicated to the XRD, ED and HREM characterization of a new bismuth copper oxyphosphate Bi_∼6.2Cu_∼6.2O₈(PO₄)₅ (a=11.599(2)Å, , c=37.541(5)Å, R₁=0.0755, Rw₂₌0.174, G.S Pn2₁a). The relatively long size of its c parameter is due to the arrangement along this direction of two kinds of ribbon-like polycations formed by edge sharing O(Bi, Cu)₄ tetrahedra. The existence of such cations is characterized by the b∼5.2 Å value intrinsic to the ribbons structure and commonly found in bismuth oxyphosphate materials. In the title compound, 2-tetrahedra wide [Bi_∼2.4Cu_∼3.6O₄]^6.4+ and 3-tetrahedra wide [Bi_∼5Cu_∼3O₆]⁹⁺ ribbons are isolated by phosphate groups and alternate along c. The interstitial site created between two different sizes ribbons is occupied by Cu²⁺ cations disordered over several close crystallographic sites. The mixed Bi³⁺/Cu²⁺ nature of certain edge-of-ribbons positions induces a disorder over several configurations of the phosphate groups. The concerned oxygen atoms form the environment of the disordered interstitial Cu²⁺ cations which occupy tunnels formed by the phosphate anions. The high-resolution electron microscope study enables a precise correlation between the observed images and the refined crystal structure, evidencing the polycations visualization. Furthermore, this material being the second example of partially disordered compound similar chemical system, some topological rules can be deduced. The b-axis doubling was observed by ED and HREM and is assigned to the ordering of interstitial Cu²⁺ within tunnels cations. A partial intra-tunnel ordering was also observed.     

Platinum complexes of diazo ligands. Studies of regioselective aromatic ring amination, oxidative halogen addition and reductive halogen elimination reactions

2-(Arylazo)pyridine ligands, L1a-1c react with the salt K2[PtCl4] to give the mononuclear complexes [PtCl2(L1)](1), which readily react with ArNH2 to yield the monochloro complexes of type [PtCl(L2)](HL2= 2-[(2-(arylamino)phenyl)azo]pyridine)(2) via regioselective ortho-amine fusion at the pendent aryl ring of coordinated L1. Oxidative addition of the electrophiles Y2(Y = Cl, Br, I) to the square-planar platinum(II) complex, has led to syntheses of the corresponding octahedral platinum(IV) complexes, [PtY3(L2)](3) in high yields. Ascorbate ion reductions of the platinum(IV) complexes, , resulted in reductive halogen elimination to revert to the platinum(II) complexes almost quantitatively. Isolation of products and X-ray structure determination of the representative complexes followed all these chemical reactions. In crystal packing, the compound [PtCl2(L1c)](1c) forms dimeric units with a Pt...Pt distance of 3.699(1) A. In contrast, the crystal packing of 2b revealed that the molecules are arranged in an antiparallel fashion to form a noncovalent 1D chain to accommodate pi(aryl)-pi(pyridyl) and Pt-pi(aryl) interactions. Notably, the oxidation of [Pt(II)Cl(L2a)](2a) by I2 produced a mixed halide complex [Pt(IV)ClI2(L2a)](5), which, in turn, is reduced by ascorbate ion to produce [Pt(II)I(L2a)] with the elimination of ClI. All the platinum(II) complexes are brown, the platinum(IV) complexes, on the other hand, are green. Low-energy visible range transitions in the complexes of the extended ligand [L2]- are ascribed to ligand basedpi-pi* transitions. Cyclic voltammetric behaviour of the complexes is reported.     

Gold nanoparticles: catalyst for the oxidation of NADH to NAD(+)

Nicotinamide adenine dinucleotide is an important coenzyme involved in the production of ATP, the fuel of energy, in every cell. It alternates between the oxidized form NAD(+) and the reduced form dihydronicotinamide adenine dinucleotide (NADH) and serves as a hydrogen and electron carrier in the cellular respiratory processes. In the present work, the catalytic effect of gold nanoparticles on the oxidization of NADH to NAD(+) was investigated. The addition of gold nanoparticles was found to quench the NADH fluorescence intensities but had no effect on the fluorescence lifetime. This suggested that the fluorescence quenching was not due to coupling with the excited state, but due to changing the ground state of NADH. The intensity of the 340 nm absorption band of NADH was found to decrease while that of the 260 nm band of NAD(+) was found to increase as the concentration of gold nanoparticles increased. This conversion reaction was further supported by nuclear magnetic resonance and mass spectroscopy. The effect of the addition of NADH was found to slightly red shift and increase the intensity of the surface plasmon absorption band of gold nanoparticles at 520 nm. This gives a strong support that the conversion of NADH to NAD(+) is occurring on the surface of the gold nanoparticles, i.e. NADH is surface catalyzed by the gold nanoparticles. The catalytic property of this important reaction might have important future applications in biological and medical fields.