Chemoselective Staudinger Reactivity of Bis(azido)phosphines Supported with a π-Donating Imidazolin-2-iminato Ligand.

Synthesis and characterization of new P(III) and P(V) bis(azido)phosphines/phosphoranes supported by an ,'-bis(2,6-diisopropylphenyl) imidazolin-2-iminato (IPrN) ligand and their reactivity with various secondary and tertiary phosphines result in the formation of chiral and/or asymmetric mono(phosphinimino)azidophosphines via the Staudinger reaction. The reaction of IPrNP(N) () or IPrNP(S)(N) () with an excess of tertiary phosphine resulted in the chemoselective formation of IPrNP(N)(NPMe) () or IPrNP(S)N(NPR) (), respectively. The chemoselective Staudinger reactivity was also observed in reactions using a secondary phosphine (HPCy) to produce IPrNP(S)N[NP(H)Cy] (), which exists in equilibrium with a tautomeric IPrNP(S)N[N(H)PCy] form (), as confirmed by P-P nuclear Overhauser effect spectroscopy (NOESY). Density functional theory (DFT) calculations point to a combination of energetically unfavorable lowest unoccupied molecular orbitals (LUMOs) and the accumulation of increasing negative charge at the terminal azido-nitrogen upon a single azide-to-phosphinimine conversion that gave rise to the observed chemoselectivity.