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• W2017570119 endingPage "13610" @default.
• W2017570119 startingPage "13599" @default.
• W2017570119 abstract "Magnesium bis(hexamethyldisilazide), Mg(HMDS)(2), reacts with substoichiometric amounts of propiophenone in toluene solution at ambient temperature to form a 74:26 mixture of the enolates (E)- and (Z)-[(HMDS)(2)Mg(2)(mu-HMDS){mu-OC(Ph)=CHCH(3)}], (E)-1 and (Z)-1, which contain a pair of three-coordinate metal centers bridged by an amide and an enolate group. The compositions of (E)-1 and (Z)-1 were confirmed by solution NMR studies and also by crystallographic characterization in the solid state. Rate studies using UV-vis spectroscopy reveal the rapid and complete formation of a reaction intermediate, 2, between the ketone and magnesium, which undergoes first-order decay with rate constants independent of the concentration of excess Mg(HMDS)(2) (DeltaH++ = 17.2 +/- 0.8 kcal/mol, DeltaS++ = -11 +/- 3 cal/mol.K). The intermediate 2 has been characterized by low-temperature (1)H NMR, diffusion-ordered NMR, and IR spectroscopy and investigated by computational studies, all of which are consistent with the formulation of 2 as a three-coordinate monomer, (HMDS)(2)Mg{eta(1)-O=C(Ph)CH(2)CH(3)}. Further support for this structure is provided by the synthesis and structural characterization of two model ketone complexes, (HMDS)(2)Mg(eta(1)-O=C(t)Bu(2)) (3) and (HMDS)(2)Mg{eta(1)-O=C((t)Bu)Ph} (4). A large primary deuterium isotope effect (k(H)/k(D) = 18.9 at 295 K) indicates that proton transfer is the rate-limiting step of the reaction. The isotope effect displays a strong temperature dependence, indicative of tunneling. In combination, these data support the mechanism of enolization proceeding through the single intermediate 2 via intramolecular proton transfer from the alpha carbon of the bound ketone to the nitrogen of a bound hexamethyldisilazide." @default.
• W2017570119 created "2016-06-24" @default.
• W2017570119 creator A5003794117 @default.
• W2017570119 creator A5028353874 @default.
• W2017570119 creator A5031370801 @default.
• W2017570119 creator A5038222645 @default.
• W2017570119 creator A5063662993 @default.
• W2017570119 date "2006-09-26" @default.
• W2017570119 modified "2023-09-30" @default.
• W2017570119 title "Kinetics and Mechanism of Ketone Enolization Mediated by Magnesium Bis(hexamethyldisilazide)" @default.
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