Highly air-stable anionic mononuclear and neutral binuclear palladium(II) complexes for C-C and C-N bond-forming reactions

The short-bite aminobis(phosphonite), PhN{P(-OC10H6(mu-S)C10H6O-)}2 (2), containing a mesocyclic thioether backbone is synthesized by either treating PhN(PCl2)2 with 2 equiv of thiobis(2,2'-naphthol) or reacting chlorophosphite (-OC10H6(mu-S)C10H6O-)PCl (1) with aniline in the presence of a base. Treatment of 2 with an equimolar amount of Pd(COD)Cl2 in the presence of H2O affords a P-N-P-bridged and P,S-metalated binuclear complex, [PhN(P(-OC10H6(mu-S)C10H6O-)-kappaP)2Pd2Cl2{P(-OC10H6(mu-S)C10H6O-)(O)-kappaP,kappaS}2] (3), whereas the same reaction with 2 equiv of Pd(COD)Cl2 in the presence of H2O and Et3N produces the mononuclear anionic complex [{(-OC10H6(mu-S)C10H6O-)P(O)-kappaP,kappaS}PdCl2](Et3NH) (5). By contrast, reaction of 2 with 2 equiv of Pd(COD)Cl2 and H2O in the absence of Et3N gives the hydrogen phosphonate coordinated complex [{(-OC10H6(mu-S)C10H6O-)P(OH)}PdCl2] (4) which converts to the anionic complex in solution or in the presence of a base. Compound 2 on treatment with Pt(COD)X2 (X = Cl or I) afforded P-coordinated four-membered chelate complexes [PhN(P(-OC10H6(mu-S)C10H6O-)-kappaP)2PtX2] (6 X = Cl, 7 X = I). The crystal structures of compounds 2, 3, 5, and 7 are reported. Compound 3 is the first example of a crystallographically characterized binuclear palladium complex containing a bidentate bridging ligand and its hydrolyzed fragments forming metallacycles containing a palladium-phosphorus sigma bond. All palladium complexes proved to be very good catalysts for the Suzuki-Miyaura and Mizoroki-Heck cross-coupling and amination reactions with excellent turnover numbers (TON up to 1.46 x 105 in the case of the Suzuki-Miyaura reaction).     

Copper(I) complexes of bis(2-(diphenylphosphino)phenyl) ether: synthesis, reactivity, and theoretical calculations

The tricoordinated cationic Cu(I) complex [Cu(kappa2-P,P'-DPEphos)(kappa1-P-DPEphos)][BF4] (1) (DPEphos = bis(2-(diphenylphosphino)phenyl) ether) containing a dangling phosphorus center was synthesized from the reaction of [Cu(CH3CN)4][BF4] with DPEphos in a 1:2 molar ratio in dichloromethane. When complex 1 is treated with MnO2, elemental sulfur, or selenium, the uncoordinated phosphorus atom undergoes oxidation to form a P=E bond resulting in the formation of complexes of the type [Cu(kappa2-P,P'-DPEphos)(kappa2-P,E-DPEphos-E)][BF4] (2, E = O; 3, E = S; 4, E = Se) containing a Cu-E bond. The zigzag polymeric CuI complex [Cu(kappa2-P,P'-DPEphos)(micro-4,4'-bpy)]n[BF4]n (5) was prepared by the reaction of [Cu(CH3CN)4][BF4] with DPEphos and 4,4'-bipyridine in an equimolar ratio. The stereochemical influences of DPEphos on its coordination behavior are examined by density functional theory calculations.     

Choice of Reference Electrode is Critical for Potentiometric Whole Cell‐based Sensor

Cells have a net negative outer charge which gives rise to a potential difference in a potentiometric set up. Here, Triton X‐100 was used as a model toxin and the cell death was monitored by the potential change, noticed as decrease in negativity. Hence, cytotoxicity can be tested in vitro and real‐time using potentiometry. However, silver ions (Ag⁺) and/or silver chloride ions (AgCl₂)^?1 lead to cell death when we used the standard Ag/AgCl reference electrode with 3 M NaCl as filling solution. Our further experimentation showed that PBS as filling solution was biocompatible and also gave stable potentiometric profiles.     

Synthesis and antioxidant activity study of carbothioamide and their corresponding thiazole derivatives

A novel series of 5-(p-(prop-2-ynyloxy)phenyl)-3-aryl-4,5-dihydropyrazole-1-carbothioamides 2a-f and functionalized 2-(3-(aryl)-5-(4-(prop-2-ynyloxy)phenyl)-4,5-dihydropyrazol-1-yl)-4-(3-arylsydnone-4-yl)thiazoles 4a-l were synthesized. The newly synthesized compounds were elucidated by analytical and spectral analysis. From the single-crystal X-ray diffraction method, it was observed that 2d crystallizes in a monoclinic crystal system with P21/n space group. The compounds 2d crystallized with cell parameters a = 15.0614 (19) Å, b = 6.0805 (7) Å, c = 20.903 (7) Å, α = 114.136 (6)^o, β = 110.709 (14) ^o, γ = 96.553 (5) ^o, V = 1790.6 (4) ų, Z = 4. From the Hirshfeld surface computational method, the major intercontacts present in these molecules are H…H (31.6%), C…H (18.2%) and S…H (12.2%), respectively. The newly synthesized compounds were tested for their ability to bleach 2,2'-diphenyl-1-picrylhydrazyl (DPPH) radical using DPPH scavenging assay. Among the synthesized compounds carbothioamide compounds 2c (90.7%) and 2b (89.8%) exhibited good DPPH scavenging activity compared to the rest of the compounds. Most of the synthesized carbothioamide molecules ( 2a-f ) found to be potent compared to the thiazole derivatives ( 4a-l ).     

Microwave mediated synthesis of non-carboxylic analogues of ibuprofen with improved pharmacological activity

A series of 1,2,4-triazolo[3,4-b]-thiadiazoles were synthesized following microwave irradiation method and also by conventional method.Newly synthesized compounds were evaluated for their anti-inflammatory and analgesic activities.     

New hexaphosphane ligands 1,3,5-C6H3{p-C6H4N(PX2)2}3 [X = Cl, F, C6H3OMe(C3H5)]: synthesis, derivatization and palladium(II) and platinum(II) complexes

A novel dodecachlorohexaphosphane, 1,3,5-C(6)H(3)[p-C(6)H(4)N(PCl(2))(2)](3) (1) was synthesized by reacting 1,3,5-tris(4'-anilino)benzene with phosphorus trichloride. Fluorination of 1 with SbF(3) produces 1,3,5-C(6)H(3)[p-C(6)H(4)N(PF(2))(2)](3) (2). The derivatization of chlorohexaphosphane with an aryloxy substituent and its palladium(II) and platinum(II) complexes are also described.     

Tracing the sources of water using stable isotopes: first results along the Mangalore-Udupi region, south-west coast of India

The Mangalore and Udupi region on the south-west coast of India is characterized by small west-flowing rivers (150-250 km in length) originating in the Western Ghats (up to 1940 meters above sea level (m asl)) and joining the Arabian Sea. The area experiences a humid tropical climate with frequent, high-intensity rainfall (4000 mm annual average). Nevertheless, there is a shortage of water during the peak dry season immediately before the onset of monsoon because of a rapid fall in the groundwater level. From the humid high-altitude forests to the intense agriculture in the coastal area, there is an urgent need to understand the movement of water between evapotranspiration, rainfall, river systems and the groundwater compartments in order to achieve better water resource management. Demographic pressure on the area with over half a million inhabitants and industrial activity strongly influence this fragile ecosystem. The coastal area is characterized by shallow open wells, which are particularly sensitive to pollution and eutrophication. Stable water isotopes ((18)O and deuterium) were used for the first time in this region to determine the isotopic characteristics of the different waters. There is a clear seasonal difference in the isotopic ratios and d-excess values between the summer and winter monsoon periods, with a predominance of lighter isotopes in the latter period. No significant variations in isotopic ratios were observed in relation to altitude because of the possible role of mist formation at high altitude. Greater d-excess values were observed in the west-flowing streams than in rivers flowing east on account of the moist westerly oceanic winds and water vapour recycling.     

Elucidation of cell killing mechanism by comparative analysis of photoreactions on different types of bacteria

The mechanism of biocidal action of nano titania on Escherichia coli and Staphylococcus aureus has been evaluated by various biochemical techniques like lipid peroxidation, hydrolysis of orthonitrophenol β-D-galactopyranoside, estimation of protein-amino acid and bacterial nucleic acids leakage into solution, in addition to morphology studies by electron microscopy (TEM and SEM) and K(+) ion leakage by inductively coupled plasma optical emission spectrometry. The active anatase phase of nano titania has been synthesized by sol-gel and pulverization techniques to obtain particle sizes averaging around 11 nm. The nano semiconductor with a bandgap of 3.2 eV responds well to the UV source to liberate reactive oxygen species (ROS). Gram negative bacteria easily succumb to the ROS at a faster rate than gram-positive bacteria with an observable difference in the mode of attack. The use of analytical techniques revealed the release of peroxidized lipid (26 nmol mL(-1) ) and protein content (370 μg mL(-1)) with a K(+) ion concentration of 22 000 ppb on complete destruction of E. coli.     

Sequential C-N and C-O bond formation in a single pot: synthesis of 2H-benzo[b][1,4]oxazines from 2,5-dihydroxybenzaldehyde and amino acid precursors

Functionalized β-aryl alanine ester derivatives were found to undergo rapid C-N and C-O bond formation with quinol carbonyl compounds to afford 2H-benzo[b][1,4]oxazines in good to excellent yields. This unprecedented finding reported herein offers a straightforward, highly efficient, and rapid method for the synthesis of 2H-benzo[b][1,4]oxazines.     

Structural and luminescence properties of Dy3+ ion in strontium lithium bismuth borate glasses

Different concentrations of dysprosium doped strontium lithium bismuth borate (SLBiB) glasses were synthesized by the conventional melt quenching method and characterized through X-ray diffraction, Raman, absorption and visible luminescence spectroscopies. These Dy³⁺ doped glasses are studied for their utility for white light emitting diodes. X-ray diffraction studies revealed amorphous nature of the studied glass matrices. Coexistence of trigonal BO₃ and tetrahedral BO₄ units was evidenced by Raman spectroscopy. From the absorption spectra, Judd–Ofelt (J–O) intensity parameters, Ω_λ (λ=2, 4 and 6), have been calculated. The hypersensitivity of the transition, ⁶H_15/2→⁶F_11/2 of Dy³⁺ has been discussed based on the magnitude of Ω₂ parameter. Using J–O intensity parameters, several radiative properties such as spontaneous transition probabilities (A_R), radiative branching ratios (β_R) and radiative lifetimes (τ_R) have been determined. From the emission spectra, a strong blue emission that corresponds to the transition, ⁴F_9/2→⁶H_15/2, was observed and it also shows combination of blue, yellow and red emission bands for these glasses. In addition to that, white light emission region have been observed from these studies.