Rate Constants for Hydrogen Atom Transfer Reactions from Bis(cyclopentadienyl)titanium(III) Chloride-Complexed Water and Methanol to an Alkyl Radical.

[摘要]：Rate consts. for hydrogen atom transfer reactions of the water, deuterium oxide, and methanol complexes of bis(cyclopentadienyl)titanium(III) chloride with the secondary alkyl radical 1-cyclobutyldodecyl (2) were detd. using indirect kinetic methods. The rate const. for reaction of Cp2TiIIICl-H2O in THF at ambient temp. was 1.0 ?105 M-1 s-1, and the kinetic isotope effect was kH/kD = 4.4. In benzene contg. 0.95 M methanol, the rate const. for reaction of the Cp2TiIIICl-MeOH at ambient temp. was 7.5 ?104 M-1 s-1. An Arrhenius function for reaction of the Cp2TiIIICl-H2O complex in THF was log k = 9.1 - 5.5/2.3RT (kcal/mol). The entropic term for reaction of Cp2TiIIICl-H2O was normal, whereas the entropic term previously found for reaction of the Et3B-H2O complex with radical 2 was unusually small (Jin, J.; Newcomb, M. J. Org. Chem.2007, 72, 5098).

[全文传递流程]：

一般上传文献全文的时限在1个工作日内