What are the pKa values of organophosphorus compounds?

A first-principle theoretical protocol was developed, which could successfully predict the pK(a) values of a number of amines and thiols in DMSO with a precision of about 1.1 pK(a) unit. Using this protocol we calculated the pK(a) values of diverse types of organophosphorus compounds in DMSO. The accuracy of these predicted values was estimated to be about 1.1 pK(a) because phosphorus is ill the same group as nitrogen and in the same period as sulfur. The theoretical predictions were also consistent with all the available experimental data. Thus, a scale of reliable pK(a) values was constructed for the first time for organophosphorus. These pK(a) values would be helpful to synthetic chemists who need to design the experimental conditions for handling deprotonated organophosphorus. On the basis of these pK(a) Values we also studied, for the first time, some interesting topics such as the substituent effects on the pK(a) values of various types of organophosphorus, and the differences between the pK(a) values of organophosphorus and organic amines. (c) 2006 Elsevier Ltd. All rights reserved.