Biomimetic cleavage of RNA models promoted by a dinuclear Zn(II) complex in ethanol. Greater than 30 kcal/mol stabilization of the transition state for cleavage of a phosphate diester.
作者： C. Tony Liu , Alexei A. Neverov , R. Stan Brown
DOI: 10.1021/JA806462X
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摘要: The cleavage of a series seven substituted aryl 2-hydroxypropyl phosphates (1a−g) promoted by dinuclear Zn(II) complex (3:Zn(II)2:(−OCH2CH3)) was investigated in ethanol at ss pH 9.0 ± 0.2 and 25 °C. kinetics for appearance the product phenols follow very strong saturation behavior all substrates where dissociation constant bound has an upper limit Km = 3 × 10−7 M kcatmax corr. values (corrected triflate inhibition) range from 168 to s−1. A partial sspH/log profile 3:Zn(II)2:(−OCH2CH3)-catalyzed reaction 1e (3-methoxyphenyl phosphate) is bell-shaped, plateauing 7.9−10, fit two kinetically important ionizations having sspKa 7.22 10.9. Bronsted plot log (kcatmax corr.) vs shows break about 14.3 with βlg −1.12 0.0. This analyzed terms change rate limiting step phosphate conformational ...
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