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| - Application of the NT Solvent Nucleophilicity Scale To Attack atPhosphorus: Solvolyses ofN,N,N‘,N‘-Tetramethyldiamidophosphorochloridate
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| - The specific rates of solvolysis of N,N,N‘,N‘-tetramethyldiamidophosphorochloridate have beenmeasured at 25.0 °C in 31 solvents. Analysis with the extended Grunwald−Winstein equation leadsto sensitivities toward changes in solvent nucleophilicity (l) of 1.20 ± 0.07 and toward changes insolvent ionizing power (m) of 0.69 ± 0.04. The correlation is improved by omission of the four datapoints for 2,2,2-trifluoroethanol−ethanol mixtures (F-test value from 155 to 320) with very smallreductions in both l and m values. Activation parameters are reported for eight of the solvolyses.The l and m values are very similar to those previously reported for solvolyses of severalarenesulfonyl chlorides, consistent with a concerted substitution process. This assignment issupported by a large kCl/kF ratio for hydrolysis and a corresponding ratio for hydroxide-assistedhydrolysis of 178. The stereochemistry of nucleophilic attack at tetracoordinate phosphorus(V) isdiscussed.
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