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- W2127307145 abstract "The kinetics and mechanism of the pyridinolysis <TEX>$(XC_5H_4N)$</TEX> of Y-aryl phenyl isothiocyanophosphates (1;<TEX>$(YC_6H_4O);(C_6H_5O)$</TEX>P(=O)NCS) are investigated in acetonitrile at 55.0 ℃. The Hammett plots for substituent (Y) variations in the substrate (log k₂ vs σY) exhibit a convex upward biphasic type with breaks at Y = H. For electron-donating Y groups the Hammett coefficients, ρY, are positive and cross-interaction constant ρXY is negative, while those for electron-withdrawing Y groups ρY values are negative with a positive ρXY. These results are interpreted to indicate mechanistic change at the breakpoint (σY = 0) from a concerted to a stepwise mechanism with rate-limiting expulsion of the <TEX>$^-NCS$</TEX> group from a trigonal bipyramidal pentacoordinated (TBP-5C) intermediate. Biphasic plots of log k₂ vs σX or <TEX>$pK_a$</TEX>(X) with steeper slopes for the more basic nucleophiles are obtained suggesting an equatorial nucleophilic attack in contrast to an apical attack for the less basic nucleophiles with smaller magnitude of ρX or βx." @default.
- W2127307145 created "2016-06-24" @default.
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- W2127307145 date "2003-08-20" @default.
- W2127307145 modified "2023-10-02" @default.
- W2127307145 title "Kinetics and Mechanism of the Pyridinolysis of Aryl Phenyl Isothiocyanophosphate in Acetonitrile" @default.
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- W2127307145 doi "https://doi.org/10.5012/bkcs.2003.24.8.1135" @default.
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