Multinuclear NMR Investigations of the Oxygen, Water, and Hydroxyl Environments in Sodium Hexaniobate

Alam, Todd M.; Nyman, May; Cherry, Brian R.; Segall, Judith M.; Lybarger, Leslie E.

doi:10.1002/chin.200428012

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“…Analysis of the standard Mulliken charges reveals the known trend in basicity of the various oxygen sites in the PONb: the calculated atomic charges are −0.943e, −0.994e, and −1.137e for the terminal, central, and bridging oxygen atoms, respectively. As shown in earlier experiments 47 and calculations, 40 the bridging oxygen is the most basic of the exposed atoms of the PONb. Also depicted in Figure 1 is the optimum structure of (S)-Sarin, the enantiomer of higher toxicity 48 used in all calculations of this work.…”

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confidence: 58%

Reaction Mechanism of Nerve-Agent Hydrolysis with the Cs₈Nb₆O₁₉ Lindqvist Hexaniobate Catalyst

et al. 2016

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We present a detailed mechanism for the hydrolysis of Sarin catalyzed by Cs 8 Nb 6 O 19 obtained using electronic structure calculations. The initial steps of the reaction involve the adsorption of water and Sarin on the hexaniobate catalyst via nonbonding interactions. Dissociation of the coordinated water molecule generates a hydroxide ion that adds nucleophilically to the coadsorbed Sarin molecule in a concerted manner, following a general base catalysis mechanism. The addition of OH − to the nerve agent generates a trigonal bipyramidal pentacoordinated phosphorus intermediate that subsequently undergoes facile dissociation forming either HF or isopropanol and a corresponding phosphonic acid. The rate-determining step of the overall reaction is found to be the dissociation of water on the catalyst in concert with the nucleophilic addition of the nascent OH − to the nerve agent. The calculated barrier for this step is considerably smaller than that measured for bulk base hydrolysis. This work represents a blueprint for future studies aimed to optimize catalysts for base hydrolysis of nerve agents at the gas−surface interface.

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Section: ■ Resultssupporting

confidence: 58%

Reaction Mechanism of Nerve-Agent Hydrolysis with the Cs₈Nb₆O₁₉ Lindqvist Hexaniobate Catalyst

et al. 2016

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Multinuclear NMR Investigations of the Oxygen, Water, and Hydroxyl Environments in Sodium Hexaniobate

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 1 publication

References 1 publication

Reaction Mechanism of Nerve-Agent Hydrolysis with the Cs₈Nb₆O₁₉ Lindqvist Hexaniobate Catalyst

Reaction Mechanism of Nerve-Agent Hydrolysis with the Cs₈Nb₆O₁₉ Lindqvist Hexaniobate Catalyst

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Multinuclear NMR Investigations of the Oxygen, Water, and Hydroxyl Environments in Sodium Hexaniobate

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 1 publication

References 1 publication

Reaction Mechanism of Nerve-Agent Hydrolysis with the Cs8Nb6O19 Lindqvist Hexaniobate Catalyst

Reaction Mechanism of Nerve-Agent Hydrolysis with the Cs8Nb6O19 Lindqvist Hexaniobate Catalyst

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Reaction Mechanism of Nerve-Agent Hydrolysis with the Cs₈Nb₆O₁₉ Lindqvist Hexaniobate Catalyst

Reaction Mechanism of Nerve-Agent Hydrolysis with the Cs₈Nb₆O₁₉ Lindqvist Hexaniobate Catalyst