We describe the synthesis of geometrically distorted iminophosphoranes (1=NAr  ) by Staudinger reduction of aryl azides by the planar O,N,O-phosphabicyclic compound 1  . X-ray crystallographic analysis shows that the iminophosphoranes exist as cyclodiphosphazanes (2  ) in the solid state. Dissociation of the dimer in solution is evident in the NMR spectra for 1=NAr  ; the monomer-dimer equilibria were analyzed as a function of aryl substituent. We describe the reactivity of these compounds with respect to small molecules including silanes and boranes, wherein we observe the addition of the B-H and Si-H bonds to the polar P=NR formal double bond yielding phosphoranes (3)  . The role of the chelating ONO structure in facilitating the observed reactivity will be discussed.

Bond activation by iminophosphoranes with geometrically constrained phosphorus platform

248th National Meeting (2014)

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