Nitrous oxide as a nucleophile in the formation of a new reactive intermediate from benzyl cations in the solvolysis of benzyl azoxytosylate

The Vapor Phase Radiolysis of Isopropanol and Water–Isopropanol Mixtures. II. Nitrous Oxide as Electron Scavenger

Canadian Journal of Chemistry ◽

10.1139/v71-484 ◽

1971 ◽

Vol 49 (17) ◽

pp. 2909-2912 ◽

Cited By ~ 2

Author(s):

M. G. Bailey ◽

R. S. Dixon

Keyword(s):

Nitrous Oxide ◽

Vapor Phase ◽

Electron Attachment ◽

Hydrogen Yield ◽

Reactive Intermediate ◽

Secondary Species ◽

Electron Yield ◽

Electron Scavenger ◽

Vapor Mixtures ◽

Reaction With Water

Nitrous oxide reduces the hydrogen yield from water–isopropanol vapor mixtures by complete scavenging of electrons. Nitrogen is produced over the whole concentration range but the yield at higher isopropanol concentrations is much greater than the electron yield. The results indicate a competition between water and isopropanol for a secondary species resulting from electron attachment to N2O. Reaction of this species with isoprooanol leads to further N2 whereas reaction with water does not. The reactive intermediate is most probably N2O− or N2O2−.

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

10.33774/chemrxiv-2021-xz4qh ◽

2021 ◽

Author(s):

André Eckhardt ◽

Martin-Louis Riu ◽

Peter Müller ◽

Christopher Cummins

Keyword(s):

Nitrous Oxide ◽

Half Life ◽

Negative Charge ◽

Activation Enthalpy ◽

Activation Entropy ◽

Order Kinetic ◽

Reactive Intermediate ◽

First Order ◽

Frustrated Lewis Pair ◽

Good Agreement

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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