1,1′-Bifunctional Aminophosphane Complexes via N–H Bond Insertions of a Li/Cl Phosphinidenoid Complex and First Studies on N/P Mono Functionalizations

Syntheses of 1,1′-bifunctional aminophosphane complexes 3–10 was achieved by reacting Li/Cl phosphinidenoid complex 2 (R = CPh₃) with secondary (Me₂NH, Et₂NH, Bn₂NH, pyrrolidine, and piperidine), primary amines (EtNH₂ and allyl amine), and ammonia. Furthermore, regioselective N-silylation of 11 (R = Me) was achieved using MeLi and Me₃SiCl to give complex 12. In contrast, treatment of complex 6 with KHMDS in the presence of 18-crown-6 yielded K/NMe₂ phosphinidenoid complex 13 subsequently reacted with MeI to give P–Me substituted 14. Complex 5 was deprotonated with KHMDS in the presence of 18-crown-6 and reacted with [Ph₃C]­BF₄ to yield complex 17 via single-electron transfer reaction and P,C-heterocoupling. Finally, selective P–N bond cleavage was achieved by treating complex 18 (R = t-Bu) with HCl­(g) to afford chlorophosphane complex 19.