A quantum mechanistic investigation into the unusual reactions of nitrilimine and nitrile oxide with 2,3,4,5-tetraphenylcyclopentadienone.

Context: The theoretical study investigates the [3 + 2] cycloaddition (32CA) reactions between C, N-diphenyl nitrilimine with 2,3,4,5-tetraphenylcyclopentadienone and benzonitrile oxide with 2,3,4,5-tetraphenylcyclopentadienone. Nitrilimines and nitrile oxides are dipoles used in the synthesis of several heterocyclic compounds, including spiropyrazoline oxindoles and isoxazolines. The derivatives of these compounds are found with different biological activities, such as ion channel blockers, anti-inflammatory and anticancer agents as well as antimalarial.

The catalytic hydrogenolysis of compounds derived from guaiacol on the Cu (111) surface: mechanisms from DFT studies.

Pyrolysis oils have inferior properties compared to liquid hydrocarbon fuels, owing to the presence of oxygenated compounds such as guaiacol, CH(OH)(OCH). The catalytic hydro-deoxygenation (HDO) of phenolic compounds derived from guaiacol, catechol, phenol and anisole were investigated over the Cu (111) surface to unravel the elementary steps involved in the process of bio-oil upgrade. The phenolic compounds adsorb through their π systems to the surface, where steric effects of the methoxy group reduce the stability of anisole on the surface.

A quantum mechanistic insight into the chemo- and regio-selective [3 + 2]-cycloaddition reaction of aryl hetaryl thioketones with diazoalkanes and nitrile oxide derivatives.

In this quantum mechanistic study, density functional theory computations at the B3LYP hybrid level of theory, in addition to triple zeta basis set 6-311G (d, p), were utilized to investigate the chemoselectivities and regioselectivities of the [3 + 2] cycloaddition reaction of phenyl (2-thienyl) thioketone (B1) derivatives with nitrile oxide (B2) and diazopropane derivatives (B3). From the computations obtained, the reactions of nitrile oxide and diazopropane derivatives with phenyl (2-thienyl) thioketone proceed through an asynchronous one-step mechanism. The initial [3 + 2] cycloaddition reaction of B1 and B3 is followed by a nitrogen extrusion which is also highly asynchronous.

A review on the computational studies of the reaction mechanisms of CO conversion on pure and bimetals of late 3d metals.

Despite series of experimental studies that reveal unique activities of late 3d transition metals and their role in microorganisms known for CO conversion, these surfaces are not industrially viable yet. An insight into the elementary steps of surface catalytic processes is crucial for effective surface modification and design. The mechanisms of CO transformation into CO, through the reverse water gas shift and methane reforming, are being studied.

CO activation and dissociation on the low miller index surfaces of pure and Ni-coated iron metal: a DFT study.

We have used spin polarized density functional theory calculations to perform extensive mechanistic studies of CO dissociation into CO and O on the clean Fe(100), (110) and (111) surfaces and on the same surfaces coated by a monolayer of nickel. CO chemisorbs on all three bare facets and binds more strongly to the stepped (111) surface than on the open flat (100) and close-packed (110) surfaces, with adsorption energies of -88.7 kJ mol, -70.