Oxygen-assisted water partial dissociation on copper: a model study

2015 ◽  
Vol 17 (12) ◽  
pp. 8231-8238 ◽  
Author(s):  
Ying-Qi Wang ◽  
Li-Fen Yan ◽  
Gui-Chang Wang
Keyword(s):  
High Activity ◽  
Strong Acid ◽  
Water Dissociation ◽  
Acid Base ◽  
Base Interaction ◽  
Model Study ◽  
Partial Dissociation ◽  
Acid Base Interaction

The strong acid–base interaction, corresponding to the high activity in water dissociation.

scholarly journals SPECIFIC NATURE OF ACID-BASE INTERACTION OF OCTA(4-TERT-BUTYLPHENYL)TETRAPYRAZINOPORPHYRAZINE WITH ORGANIC PROTON-ACCEPTOR MOLECULES IN BENZENE

2021 ◽  
Vol 64 (3) ◽  
pp. 33-40
Author(s):  
Oleg A. Petrov ◽  
Aleksandr S. Semeykin ◽  
Mariya V. Shilovskaya ◽  
Tatiana V. Lyubimova
Keyword(s):  
Proton Transfer ◽  
Proton Acceptor ◽  
Base System ◽  
Excess Charge ◽  
Hydrogen Atoms ◽  
Acid Base ◽  
Base Interaction ◽  
Base Equilibrium ◽  
Acid Base Equilibrium ◽  
Acid Base Interaction

The reaction of acid-base interaction of octa(4-tert-butylphenyl)tetrapyrazinophosphyrazine with pyridine, 2-methylpyridine, morhpoline, pipyridine, n-butylamine, tert-butylamine, diethylamine, triethylamine and dimethylsulfoxide in benzene was investigated. It is shown that the researched porphyrazine forms kinetically stable proton transfer complexes with pyridine, 2-methylpyridine, morpholine and dimethylsulfoxide. In benzene-base system an acid-base equilibrium between the molecular form of octa(4-tert-butylphenyl)tetrapyrazinoporphyrazine and its proton transfer complex was established. The interaction of substituted tetrapyrazinoporphyrazine with morpholine in benzene was revealed to be a kinetically controllable process which occurs with low reaction rate and high values of activation energy. Such values are not inherent to most of relatively simple liquid-phase acid-base systems. The kinetic equation of the process was found, and, based on the spectral changes accompanying the reaction, a cheme of two-stage process of proton transfer of NH-groups of octa(4-tert-butylphenyl)tetrapyrazinoporphyrazine to morpholine in benzene was proposed. A possible structure of proton transfer complex of octa(4-tert-butylphenyl)tetrapyrazinoporphyrazine with organic bases is shown. In these complexes the inner hydrogen atoms of the cycle, bonded with base molecules, lie under and above the plane of the molecule, and the proton transfer from acid to base is limited either by the H-complex or the ion-ion associates constituting an H-bonded ion pair. Depending on the proton accepting tendency of the base, the acid-base equilibrium can shift towards or away from the more or less polarized structure. It was revealed that in benzene - n-butylamine (tri-butylamine, diethylamine, triethylamine, pipyridine) system the acid-base interaction involving octa(4- tert-butylphenyl)tetrapyrazinoporphyrazine occurs incredibly fast, with rates not measurable by standard spectrophotography methods. The forming proton transfer complexes are highly labile due to concurrent proton reaction occurring, leading to the formation of dianion form of octa(4- tert-butylphenyl)tetrapyrazinoporphyrazine. This form undergoes spontaneous dissolution into low-molecular colorless products due to the lack of compensation of excess charge in the macrocycle.

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