Halocyanophosphines P(CN)yX3-y and Related Cyanophosphine Derivatives
American Chemical Society
Using pyridine and boron trifluoride as reference compounds and 31P and 13C NMR as reaction probes, we have shown that P(CN)3 is acidic, P(CN)2(Ph) is essentially neutral, and PCN(Ph)2 is slightly basic. It is known that P(Ph)3 is a δ base. It was also possible to show that P(CN)2N(C2H5)2 is markedly basic; 13C and 31P parameters are given. Attempts to make P(CN)yCl3-y by scrambling reactions, by replacement of N(C2H5)2 with Cl by treatment of P(CN)2N(C2H5)2 with HCl, and by treating P(CN)3 with HC1 indicated that chlorocyanophosphines disproportionate at temperatures as low as -80°C to give PCl3 and P(CN)3. This phenomenon is explained in terms of an intermolecular interaction which sets up the transition state for the scrambling process.