3/2-order chain kinetics involving a postulated dicationic intermediate in the isomerization of a p-isocyano to a p-cyano azaphosphatrane monocation

Kinetic evidence suggests the possibility of a dicationic intermediate in the title reaction. Thus the linkage isomerization reaction, PNC+ = PCN+, is described by the rate law, nu = 3/2kPNC+]3/2, which can be interpreted by a chain mechanism with the propagation reaction PNC+ + P2+ --> P2+ + PCN+. Such propagation is unusual in that the intermediate regenerates itself in this single step rather than forming a different intermediate for a second propagation step. Cyanide ions inhibit the rate because they participate in the termination step, P2+ + CN- --> PCN+. The rate constant in CD3CN at 100 degrees C is 3/2k = 7.2 +/- 0.6 x 10-5 L1/2 mol-1/2 s-1; 3/2k represents the composite (kinit/kterm)1/2 kprop. When the reaction is carried out in the presence of PBr+, however, the reaction becomes much faster and is described by the rate law, nu = kBrPBr+]PNC+]; because PBr+] remains at constant concentration, the time-course experiments follow first-order kinetics.