Frustrated Lewis Pair Stabilized Phosphoryl Nitride (NPO), a Monophosphorus Analogue of Nitrous Oxide (N2O)

Phosphoryl nitride (NPO) is a highly reactive intermediate, and its chemistry has only been explored under matrix isolation conditions so far. Here we report the synthesis of an anthracene (A) and phosphoryl azide based molecule (N3P(O)A) that acts as a molecular synthon of NPO. Experimentally, N3P(O)A dissociates thermally with a first-order kinetic half-life that is associated with an activation enthalpy of Delta H+ = 27.5 +/- 0.3 kcal mol(-1) and an activation entropy of Delta S+ = 10.6 +/- 0.3 cal mol(-1) K-1 that are in good agreement with calculated DLPNO-CCSD(T)/cc-pVTZ//PBE0-D3(BJ)/cc-pVTZ energies. In solution N3P(O)A undergoes Staudinger reactivity with tricyclohexylphosphine (PCy3) and subsequent complexation with tris(pentafluorophenyl)-borane (B(C6F5)(3), BCF) to form Cy3P-NP(A)O-B(C6F5)(3). Anthracene is cleaved off photochemically to form the frustrated Lewis pair (FLP) stabilized NPO complex Cy3P circle plus - N=P-O-B-circle minus(C6F5)(3). An intrinsic bond orbital (IBO) analysis suggests that the adduct is zwitterionic, with a positive and negative charge localized on the complexing Cy3P and BCF, respectively.

Automated summary

This study describes the synthesis of a molecular synthon of phosphoryl nitride (NPO), N3P(O)A, which dissociates thermally to form a stable NPO complex. The experimental results are in good agreement with calculated energies, and the complex shows a zwitterionic nature with positive and negative charges localized on specific components.