The nucleophilic substitution reactions of Y-O-aryl methyl phosphonochloridothioates with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated kinetically in acetonitrile at 55.0 degrees C. The Hammett and Bronsted plots for substituent (X) variations in the nucleophiles are biphasic concave downwards with a break region between X = H and 4-Cl. The deuterium kinetic isotope effects (DKIEs) are primary normal (k(H)/k(D) = 1.03-1.30) for stronger nucleophiles (X = 4-MeO, 4-Me and H), and extremely large secondary inverse (k(H)/k(D) = 0.367-0.567) for weaker nucleophiles (X = 4-Cl, 3-Cl and 3-NO2). The cross-interaction constants are negative (rho(XY(H)) = -0.95 and rho(XY(D)) = -1.11) for stronger nucleophiles, while positive (rho(XY(H)) = +0.77 and rho(XY(D)) = +0.21) for weaker nucleophiles. These kinetic results indicate that the mechanism changes from a concerted process involving frontside nucleophilic attack for stronger nucleophiles to a stepwise process with a rate-limiting leaving group expulsion from the intermediate involving backside attack for weaker nucleophiles. A hydrogen-bonded, four-center-type transition state (TS) is suggested for a frontside attack, while a trigonal bipyramidal pentacoordinate TS is suggested for a backside attack. The unusually small DKIEs, as small as or equal to 0.4, for weaker nucleophiles seem to be ascribed to severe steric congestion in the TS.