Anilinolysis of Diphenyl Thiophosphinic Chloride and Theoretical Studieson Various R1R2P(O or S)Cl¢Ó

Bulletin of the Korean chemical society

Hai Whang Lee¹  In-Suk Han¹  Nilay Kumar Dey¹ 

关键词: Anilinolysis of diphenyl thiophosphinic chloride;    Frontside nucleophilic attack;    Deuterium kinetic isotope effect;    NBO charge;    Degree of distortion;   

DOI  :  

学科分类：化学（综合）

来源: Korean Chemical Society

【 摘 要 】

The aminolysis of diphenyl thiophosphinic chloride (2) with substituted anilines in acetonitrile at 55.0 oC is investigated kinetically. Kinetic results yield large Hammett �?_X (�?_nuc = ?3.97) and Bronsted �?_X (�?_nuc = 1.40) values. A concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state is proposed on the basis of the primary normal kinetic isotope effects (kH/kD = 1.0-1.1) with deuterated aniline (XC₆H₄ND₂) nucleophiles. The natural bond order charges on P and the degrees of distortion of 42 compounds: chlorophosphates [(R₁O)(R₂O)P(=O)Cl], chlorothiophosphates [(R₁O)(R₂O)P(=S)Cl], phosphonochloridates [(R₁O)R₂P(=O)Cl], phosphonochlorothioates [(R₁O)R₂P(=S)Cl], chlorophosphinates [R₁R₂P(=O)Cl], and chlorothiophosphinates [R₁R₂P(=S)Cl] are calculated at the B3LYP/ 6-311+G(d,p) level in the gas phase.

【 授权许可】

Unknown