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

28 October 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


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 ΔH⧧ = 27.5 ± 0.3 kcal mol–1 and an activation entropy of ΔS⧧ = 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⊕-N=P-O-B⊖(C6F5)3. 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.


phosphorus chemistry
triatomic molecules
Staudinger reaction
molecular precursors
frustrated Lewis pairs
multiple bonds

Supplementary materials

Supporting Information for "Frustrated Lewis Pair Stabilized Phosphoryl Nitride (NPO), a Mono Phosphorus Analogue of Nitrous Oxide (N2O)"
Synthesis details, characterization data, and Cartesian coordinates for computed structures.


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