Abstract The kinetic studies on the reactions of phenyl N-phenyl phosphoramidochloridate (8) with substituted anilines () and deuterated anilines () have been carried out in acetonitrile at. The obtained deuterium kinetic isotope effects (DKIEs;) are huge secondary inverse (= 0.52-0.69). A concerted mechanism is proposed with a backside attack transition state (TS) on the basis of the secondary inverse DKIEs and the variation trends of the values with X. ...