Inside Cover: Activation of CH3CN with (C2F5)3PF2 and amines

Eureka! We found it! Acetonitrile is not easily activated or even deprotonated. A combination of the strong Lewis acid (C2F5)3PF2 and triethylamine, however, is able to deprotonate CH3CN. The resulting cyanomethyl function is bound to the phosphorus moiety, affording the highly stable salt [HNEt3][P(C2F5)3F2(CH2CN)]. Using more nucleophilic secondary and primary amines instead of NEt3 leads to a phosphate featuring an amidine ligand, which formally results from hydroamination of acetonitrile by the amine. More information can be found in the Full Paper by B. Hoge et al.