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

Author(s):  
André K. Eckhardt ◽  
Martin-Louis Y. Riu ◽  
Peter Müller ◽  
Christopher C. Cummins
2011 ◽  
Vol 2 (1) ◽  
pp. 170-176 ◽  
Author(s):  
Rebecca C. Neu ◽  
Edwin Otten ◽  
Alan Lough ◽  
Douglas W. Stephan

2021 ◽  
Author(s):  
André Eckhardt ◽  
Martin-Louis Riu ◽  
Peter Müller ◽  
Christopher Cummins

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.


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Author(s):  
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Keyword(s):  

Agronomie ◽  
2002 ◽  
Vol 22 (7-8) ◽  
pp. 731-738 ◽  
Author(s):  
Roland Harrison ◽  
Sharon Ellis ◽  
Roy Cross ◽  
James Harrison Hodgson

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