The nucleophilic substitution reactions of bis(N,N-dimethylamino) phosphinic chloride (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $65.0^{circ}C$. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The magnitudes of ${ ho}_X$ (= -6.42) and ${eta}_X$ (= 2.27) values are exceptionally great. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D$ = 0.69-0.96). A concerted $S_N2$ mechanism involving a backside attack is proposed on the basis of secondary inverse DKIEs and the variation trend of the $k_H/k_D$ values with X. The anilinolyses of six phosphinic chlorides in MeCN are briefly reviewed by means of DKIEs, steric effects of the two ligands, positive charge of the reaction center phosphorus atom, and selectivity parameters to obtain systematic information on phosphoryl transfer reaction mechanism.