TADFIW水解反应机理的密度泛函理论

应用密度泛函理论(DFT)在B3LYP/6-31G(d,p)水平下对四乙酰基二甲酰基六氮杂异伍兹烷(TADFIW)甲酰基的水解反应机理进行了研究.结果表明,TADFIW上的甲酰基水解时,甲酰基被质子化,碳氧双键中的氧原子带有负电荷0.619 e,碳原子带有正电荷0.471 e,亲核试剂水分子进攻质子化甲酰基的碳原子,同...

Density Functional Theory on the Hydrolysis Mechanism of TADFIW

The hydrolysis mechanism of formoxyl of TADFIW was studied by a density-functional theory method in B3LYP/6-31G(d,p) level.The results showed that,when hydrolysis reaction of formoxyl of TADFIW took place,the oxygen atom of carbon-oxygen double bond had negative charges with 0.619e,while the carbon atom had positive charges with 0.471e in transition state.The carbon atom of formoxyl was attacked by the nucleophilic reagent water molecule.The bond length of carbon-nitrogen increased from 0.1310 mm to 0.1491 mm.One hydrogen atom of water molecule was separated from the oxygen atom and transferred to the nitrogen atom.The activation energy was 125.92 kJ/mol.The hydrolysis of the formoxyl of TADFIW easily took place from the view of thermodynamics.The transition state of the hydrolysis reaction of one acetyl was designed.The activation energy was 158.76 kJ/mol.The formoxyl had a prior reaction over acetyl in TADFIW.