Dithiolate complexes of manganese and rhenium: X-ray structure and properties of an unusual mixed valence cluster Mn3(CO)6(mu-eta2-SCH2CH2CH2S)3

Treatment of Mn(2)(CO)(10) with 3,4-toluenedithiol and 1,2-ethanedithiol in the presence of Me(3)NO.2H(2)O in CH(2)Cl(2) at room temperature afforded the dinuclear complexes Mn(2)(CO)(6)(mu-eta(4)-SC(6)H(3)(CH(3))S-SC(6)H(3)(CH(3))S) (1), and Mn(2)(CO)(6)(mu-eta(4)-SCH(2)CH(2)S-SCH(2)CH(2)S) (2), respectively. Similar reactions of Re(2)(CO)(10) with 3,4-toluenedithiol, 1,2-benzenedithiol, and 1,2-ethanedithiol yielded the dirhenium complexes Re(2)(CO)(6)(mu-eta(4)-SC(6)H(3)(CH(3))S-SC(6)H(3)(CH(3))S) (3), Re(2)(CO)(6)(mu-eta(4)-SC(6)H(4)S-SC(6)H(4)S) (4), and Re(2)(CO)(6)(SCH(2)CH(2)S-SCH(2)CH(2)S) (5), respectively. In contrast, treatment of Mn(2)(CO)(10) with 1,3-propanedithiol afforded the trimanganese compound Mn(3)(CO)(6)(mu-eta(2)-SCH(2)CH(2)CH(2)S)(3) (6), whereas Re(2)(CO)(10) gave only intractable materials. The molecular structures of 1, 3, and 6 have been determined by single-crystal X-ray diffraction studies. The dimanganese and dirhenium carbonyl compounds 1-5contain a binucleating disulfide ligand, formed by interligand disulfide bond formation between two dithiolate ligands identical in structure to that of the previously reported dimanganese complex Mn(2)(CO)(6)(mu-eta(4)-SC(6)H(4)S-SC(6)H(4)S). Complex 6, on the other hand, forms a unique example of a mixed-valence trimangenese carbonyl compound containing three bridging 1,3-propanedithiolate ligands. The solution properties of 6 have been investigated by UV-vis and EPR spectroscopies as well as electrochemical techniques.     

QbD approached comparison of reaction mechanism in microwave synthesized gold nanoparticles and their superior catalytic role against hazardous nirto‐dye

Microwave irradiation (MI) process characteristically enables extremely rapid “in‐core” heating of dipoles and ions, in comparison to conventional thermal (conductance) process of heat transfer. During the process of nanoparticles synthesis, MI both modulates functionality behaviors as well as dynamic of reaction in favorable direction. So, MI providing a facile, favorable and alternative approach during nanoparticles synthesis nanoparticles with enhanced catalytic performances. Although, conventionally used reducing and capping reagents of synthetic origin, are usually environmentally hazardous and toxic for living organism. But, in absence of suitable capping agent; stability, shelf life and catalytic activity of metallic nanoparticles adversely affected. However, polymeric templates which emerged as suitable choice of agent for both reducing and capping purposes; bearing additional advantages in terms of catalyst free one step green synthesis process with high degree of biosafety and efficiency. Another aspect of current works was to understand role of process variables in growth mechanism and catalytic performances of microwave processed metallic nanoparticles, as well as comparison of these parameters with conventional heating method. However, due to poor prediction ability with previously published architect OFAT (One factor at a time) design with these nanoparticles as well as random selection of process variables with their different levels, such comparison couldn't be possible. Hence, using gum Ghatti (Anogeissus latifolia) as a model bio‐template and under simulated reaction conditions; architect of QbD design systems were integrated in microwave processed nanoparticles to establish mechanistic role these variables. Furthermore, in comparison to conventional heating; we reported well validated mathematical modeling of process variables on characteristic of nanoparticles as well as synthesized gold nanoparticles of desired and identical dimensions, in both thermal and microwave‐based processes. Interestingly, despite of identical dimension, MI processed gold nanoparticles bearing higher efficiency (kinetic rate) against remediation of hazardous nitro dye (4‐nitrophenol), into safer amino (4‐aminophenol) analogues.     

Palladium-catalyzed regiocontrolled internal heteroarylation of electron-rich olefins with heteroaryl halides

A highly efficient palladium-catalyzed Heck coupling reaction of heteroaryl halides with electron-rich vinyl ether and hydroxyalkyl vinyl ethers is described. It was found that the choice of solvent, ligand, and reaction temperature had a fundamental influence on the regioselectivity and reactivity of the reaction, and the combination of Pd(OAc)₂ and DPPF in ethylene glycol led to the most effective catalytic system. Under these conditions, a variety of heteroaryl halides reacted very quickly with electron-rich olefins to afford exclusively the branched products in good to excellent yields without employing triflates, halide scavengers, or ionic liquids.     

Modelling and measuring the thermal conductivity of multi-metallic Zn/Cu nanofluid

A metallic nanofluid is a suspension of metallic nanoparticles in a base fluid. Multi-metallic nanoparticles are a combination of two or more types of metallic particles. Such multi-metallic nanoparticles were suspended in water using an ultrasonic vibrator for different total volume fractions and different ratios of metallic/metallic nanoparticles. A transient hot wire setup was built to measure the thermal conductivity of the nanofluid at different temperatures. The experimental results were in good agreement with the results in the literature. Then, the experimental results were used as input data for an adaptive neural fuzzy inference system (ANFIS) to predict the thermal conductivity of the multi-metallic nanofluid. The maximum deviation between the ANFIS results and experimental measurements was 1 %. The predicted results and the experimental data were compared with other models. The ANFIS model was found to have good ability to predict the thermal conductivity of the multi-metallic nanofluid over the range of the experimental results.     

Singular solutions for the constant Q-curvature problem

This paper is devoted to the construction of weak solutions to the singular constant Q-curvature problem. We build on several tools developed in the last years. This is the first construction of singular metrics on closed manifolds of sufficiently large dimension with constant (positive) Q-curvature.     

Synthesis of a new class of glycolipids and the evaluation of their immunogenicity using murine splenocytes

A new class of glycolipids were generated by the incorporation of lipid entities at the C-6 position of D-glucose through oxidation of the primary hydroxyl group of tetrabenzylated D-glucose to form corresponding aldehyde, which in turn was subjected to Grignard reaction with C8 and C16 alkyl magnesium halides. The resulting lipidated secondary alcohol was further subjected to esterification with long-chain carboxylic acids to afford novel glycolipids. All of the derivatives 4a–b, 6a–d, and 8a–b exhibited low cytotoxicity and induced strong T and B cell proliferation and IL-2, IL-4, and IFN-γ expression from stimulated splenocyte culture, signifying their potent immunostimulating activity.     

Oligomerization and regioselective hydrosilylation of styrenes catalyzed by cationic allyl nickel complexes bearing allylphosphine ligands

The complexes [Ni(eta(3)-CH(2)CHCH(2))Br(kappa(1)P-PR(2)CH(2)CH=CH(2))] (R = Ph 1, (i)Pr2 ) and [Ni(eta(3)-CH(2)C(R')CH(2))(kappa(1)P-PR(2)CH(2)CH=CH(2))(2)][BAr'(4)] (R' = H, R = Ph 4a, R = (i)Pr 4b; R' = CH(3), R = Ph 5a, R = (i)Pr 5b; Ar' = 3,5-C(6)H(3)(CF(3))(2)) have been prepared and characterized. The X-ray crystal structures of 1, 2 and 5b have been determined. 4a-b and 5a-b are catalyst precursors for the oligomerization of RC(6)H(4)CH=CH(2) to oligostyrene (R = H) or oligo(4-methylstyrene) (R = CH(3)) respectively, without the need of a co-catalyst such as methylalumoxane. The catalytic activities range from moderate to high. The oligomerization reactions are carried out in the temperature interval 25-40 degrees C in 1,2-dichloroethane, using an olefin/catalyst ratio equal to 200, yielding oligostyrenes with a high isotactic fraction content P(m), with M(n) in the range 700-1900 Dalton, and polydispersities between 1.22 and 1.64. The cationic complexes 4a-b and 5a-b are also effective catalyst precursors for the hydrosilylation reactions of styrene or 4-methylstyrene with PhSiH(3) in 1,2-dichloroethane at 40 degrees C using an olefin/catalyst ratio equal to 100, leading selectively to RC(6)H(4)CH(SiH(2)Ph)CH(3) (R = H, CH(3)) in 50-79% yield.