Silicon containing new salicylaldimine Pd(II) and Co(II) metal complexes as efficient catalysts in transformation of carbon dioxide (CO2) to cyclic carbonates

A new series of metal complexes of salicyladimine ligands with Pd(II) and Co(II) have been prepared and characterized by different techniques (elemental analysis, UV-vis, FT-IR, ¹H NMR spectra, magnetic susceptibility measurements). Electronic spectra and magnetic susceptibility measurements reveal square planar geometry for Pd(II) metal complex and tetrahedral geometry for Co(II) metal complex. The synthesized Pd(II) and Co(II) complexes were also tested as catalysts for the formation of cyclic organic carbonates from carbon dioxide and liquid epoxides which served as both reactant and solvent. The results showed that the [M(L₃)₂] (M = Pd or Co) complexes bearing 5-methyl substituent on the aryl ring are more efficient than the other Pd(II) and Co(II) metal complexes for the formation of cyclic organic carbonates from carbon dioxide. These catalysts, [Pd(L₃)₂] and [Co(L₃)₂] complexes and location (p-position of phenoxy) of electron donating methyl substituent in particular, effectively promote the of carbon dioxide activation with liquid epoxides under solvent-free homogeneous conditions. Furthermore, [Pd(L₃)₂] can be reused more than eight times with a minimal loss of its original catalytic activities.     

Multi-project scheduling with two-stage decomposition

We consider a non-preemptive, zero time lag multi-project scheduling problem with multiple modes and limited renewable and nonrenewable resources. A two-stage decomposition approach is adopted to formulate the problem as a hierarchy of 0-1 mathematical programming models. In stage one; each project is reduced to a macro-activity with macro-modes. The macro-activities are combined into a single macro-activity network over which the macro-activity scheduling problem (MP) is defined, where the objective is the maximization of the net present value with positive cash flows and the renewable resource requirements are time-dependent. An exact solution procedure and a genetic algorithm (GA) approach are proposed for solving the MP. A GA is also employed to generate an initial solution for the exact solution procedure. The first stage terminates with a post-processing procedure to distribute the remaining resource capacities. Using the start times and the resource profiles obtained in stage one, each project is scheduled in stage two for minimum makespan. Three new test problem sets are generated with 81, 84 and 27 problems each, and three different configurations of solution procedures are tested.     

Revisiting roaming trajectories in ketene isomerization at higher dimensionality

Roaming dynamics have been observed in a three-dimensional model of the ketene isomerization reaction. The roaming trajectories sample the region between the outer potential barriers closest to the respective ketene isomers and involve turning points along the reaction coordinate in a polar representation. These roaming trajectories avoid the intrinsic reaction coordinate and the intermediates to which it is associated. Thus, one-dimensional transition state theory (TST) is generally insufficient as has been confirmed through an analysis of the reactive flux along the dividing surface (DS). A global representation of the DS, however, leads to accurate TST rate constants. The exact and TST microcanonical rates of isomerization have been obtained for the three-dimensional model and compare well to experiment. The global DS is therefore particularly important for obtaining rates in reactions that exhibit roaming. This work thus confirms the findings of our previous two-dimensional treatment of ketene isomerization (Ulusoy et al. in J. Phys. Chem. A 117:7553–7560, 2013).     

Approximation by modified Szász-Durrmeyer operators

The main goal of this paper is to introduce Durrmeyer modifications for the generalized Szász–Mirakyan operators defined in (Aral et al., in Results Math 65:441–452, 2014). The construction of the new operators is based on a function \(\rho \) which is continuously differentiable \(\infty \) times on \( \left[ 0,\infty \right) ,\) such that \(\rho \left( 0\right) =0\) and \( \inf _{x\in \left[ 0,\infty \right) }\rho ^{\prime }\left( x\right) \ge 1.\) Involving the weighted modulus of continuity constructed using the function \( \rho \), approximation properties of the operators are explored: uniform convergence over unbounded intervals is established and a quantitative Voronovskaya theorem is given. Moreover, we obtain direct approximation properties of the operators in terms of the moduli of smoothness. Our results show that the new operators are sensitive to the rate of convergence to f,  depending on the selection of \(\rho .\) For the particular case \(\rho \left( x\right) =x\), the previous results for classical Szász-Durrmeyer operators are captured.     

Development of a cloud point extraction and preconcentration method for chromium(III) and total chromium prior to flame atomic absorption spectrometry

A sensitive and selective method has been developed for the determination of chromium in water samples based on using cloud point extraction (CPE) preconcentration and determination by flame atomic absorption spectrometry (FAAS). The method is based on the complexation of Cr(III) ions with Brilliant Cresyl Blue (BCB) in the presence of non-ionic surfactant Triton X-114. Under the optimum conditions, the preconcentration of 50 mL of water sample in the presence of 0.5 g/L Triton X-114 and 1.2 × 10⁻⁵ M BCB permitted the detection of 0.42 μg/L chromium(III). The calibration graph was linear in the range of 1.5–70 μg/L, and the recovery of more than 99% was achieved. The proposed method was used in FAAS determination of Cr(III) in water samples and certified water samples. In addition, the developed CPE-FAAS method was also used for speciation of the inorganic chromium species after reduction of Cr(VI) to Cr(III) using a thiosulphate solution of 120 mg/L in the presence of Hg(II) ion as a stabilizer.     

Synthesis,characterization and thermal study of some tetradentate Schiff base transition metal complexes

Several mononuclear Co(II), Ni(II), Cu(II), and Fe(II) complexes of tetradentate salpren-type diimine, obtained from 3,5-di-tert-butyl-2-hydroxybenzaldehyde and 1,3-diaminopropane have been prepared and characterized by analytical, spectroscopic (FT-IR, UV–VIS) techniques, magnetic susceptibility measurements and thermogravimetric analyses (TG). The thermodynamic and thermal properties of complexes have been investigated. For further characterization Direct Insertion Probe-Mass Spectrometry (DIP-MS) was used and the fragmentation pattern and also stability of the ions were evaluated. The characterization of the end products of the decomposition was achieved by X-ray diffraction. The thermal stabilities of metal complexes of N,N′-bis(3,5-di-t-butylsalicylidene)-1,3-propanediamine ligand (L) were found as Ni(II) > Cu(II) > Co(II) > Fe(II).     

Back Cover: Manipulating Intermetallic Charge Transfer for Switchable External Stimulus-Enhanced Water Oxidation Electrocatalysis (Angew. Chem. Int. Ed. 44/2023)

Electrocatalytic processes involving the oxygen evolution reaction (OER) present a kinetic bottleneck due to the existence of linear-scaling relationships, which bind the energies of the different intermediates in the mechanism limiting optimization. Here, we offer a way to break these scaling relationships and enhance the electrocatalytic activity of a Co−Fe Prussian blue modified electrode in OER by applying external stimuli. Improvements of ≈11 % and ≈57 % were achieved under magnetic field (0.2 T) and light irradiation (100 mW cm⁻²), respectively, when working at fixed overpotential, η=0.6 V at pH 7. The observed enhancements strongly tie in with the intermetallic charge transfer (IMCT) intensity between Fe and Co sites. Density Functional Theory simulations suggest that tuning the IMCT can lead to a change of the OER mechanism to an external stimuli-sensitive spin crossover-based pathway, which opens the way for switchable electrocatalytic devices.