Kinetics and Mechanism of the Pyridinolysis of Methyl Phenyl Phosphinic Chloride in Acetonitrile

The pyridinolysis of methyl phenyl phosphinic chloride is investigated kinetically in acetonitrile at -20.0 degrees C. The Hammett and Bronsted plots for substituent X variations in the nucleophiles are biphasic concave downwards with a break point at X = H, and unusual positive rho(X) (= 2.94) and negative beta(X) (= -0.48) values are obtained for the strongly basic nucleophiles. A stepwise mechanism with a rate-limiting step change from bond breaking for the weakly basic pyridines to bond formation for the strongly basic pyridines is proposed on the basis of biphasic concave downward Hammett and Bronsted plots. Unusual positive rho(X) and negative beta(X) values are rationalized by the isokinetic relationship. The pyridinolyses and anilinolyses of four R1R2P(=O)Cl-type substrates, dimethyl, diethyl, methyl phenyl, and diphenyl phosphinic chlorides in acetonitrile are compared to obtain systematic information on phosphoryl transfer reaction mechanism. The combination of the two ligands, Me and Ph, shows unexpected kinetic results for both the anilinolysis and pyridinolysis: greatest magnitude of k(H)/k(D) (= 2.10) involving deuterated anilines [XC6H4NH2(D-2)] for the anilinolysis, and exceptionally fast rate and biphasic concave downward free energy correlation for the pyridinolysis.