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Design and development of novel, low-cost and efficient electrocatalysts for oxygen evolution reaction (OER) in alkaline media is crucial for lowering the reaction overpotential and thus decreasing the energy input during the water electrolysis process. Herein, we present the synthesis of new 14-membered bis-thiosemicarbazide and bis-isothiosemicarbazide macrocycles and their nickel(II) complexes characterized by spectroscopic techniques (1H and 13C NMR, IR, UV–vis), electrospray ionization mass spectrometry, single crystal X-ray diffraction, scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX) and cyclic voltammetry. Finally, the activity of nickel(II) complexes towards OER is reported. NiIILSEt delivered a current density of 10 mA cm−2 at the lowest overpotential of 350 mV with the lowest Tafel slope of 93 mV dec−1. The high performance of NiIILSEt might be attributed to its high surface area and thus abundant active sites with the observed low charge-transfer resistance enabling the effective current flow through the electrocatalyst. Square-planar coordination geometry and increment in Ni oxidation state are believed to favor its OER performance. Beside high activity towards OER, NiIILSEt demonstrated excellent long-term stability with continuous operation, advocating its possible application in commercial systems. [ABSTRACT FROM AUTHOR]

A general and stereoselective five-step approach to 14-membered cyclic bis-semicarbazones, 5,12-diaryl-7,14-dimethyl-1,2,4,8,9,11-hexaazacyclotetradeca-7,14-diene-3,10-diones, starting from aldehyde semicarbazones has been developed. The key intermediates, 4-(3-oxobut-1-yl)semicarbazones, were prepared by BF 3 -catalyzed amidoalkylation of 2-(trimethylsilyloxy)propene with 4-[(aryl)(methoxy)methyl]- or 4-[(aryl)(tosyl)methyl]semicarbazones. Treatment of these intermediates with excess of hydrazine gave hydrazones of 4-(3-oxobut-1-yl)semicarbazones or 4-(3-oxobut-1-yl)semicarbazides, which in the presence of TsOH were converted into the target macrocycles. All steps of this approach could be scaled up easily to the multi-gram level.

A general approach to 6-phenylthio-substituted 2,3,4,5-tetrahydro-1H-1,3-diazepin-2-ones based on the ring expansion reaction of 1,2,3,4-tetrahydropyrimidin-2-ones under the action of nucleophiles has been developed. The first step of the synthesis was preparation of N-[(2-benzoyloxy-1-tosyl)ethyl]urea by three-component condensation of 2-benzoyloxyethanal, urea and p-toluenesulfinic acid. Nucleophilic substitution of the tosyl group in the obtained sulfone with sodium enolates of α-phenylthioketones followed by cyclization-dehydration, and debenzoylation gave 4-hydroxymethyl-5-phenylthio-1,2,3,4-tetrahydropyrimidin-2-ones which were transformed into the 4-mesyloxymethyl-derivatives. Treatment of the latter with nucleophilic reagents, such as NaCN, sodium diethyl malonate, PhSNa, MeONa, NaBH(4), sodium succinimide, or potassium phthalimide, afforded the target multi-functionalized diazepinones. The obtained 6-phenylthio-diazepinones and their 6-tosyl-substituted analogues were converted into 3-substituted 1-carbamoyl-1H-pyrroles under acidic conditions as a result of ring contraction. Effective one-pot synthesis of the latter from 4-mesyloxymethyl-pyrimidines was realized using a ring expansion/ring contraction sequence.