Olson Isabel A, Sessler Anne M, Connell Jodi L, Giordano Esthefanie, Sosa Yessica Y Baez, Zavaleta Salvador W, Bowyer Walter J
Department of Chemistry, Hobart College, Geneva, New York 14456, USA.
J Phys Chem A. 2009 Mar 26;113(12):2801-8. doi: 10.1021/jp811111e.
Indium-mediated allylation provides remarkable stereo- and regioselectivity, and it proceeds easily and in high yield in aqueous solutions. In spite of its widespread use, there have been few fundamental studies of this reaction. We have developed a photomicrographic technique for measuring rates of reaction of allyl halides at indium surfaces, and we describe the mathematical model for discriminating between diffusion and kinetic control. The measurements demonstrate that this reaction is diffusion controlled, and the minimum value of the heterogeneous rate constant is 1 x 10(-3) cm s(-1). These results broaden the applicability of photomicroscopy for measuring heterogeneous rates of reactions that result in consumption of solid metals.
铟介导的烯丙基化反应具有出色的立体选择性和区域选择性，且在水溶液中反应轻松且产率高。尽管该反应应用广泛，但对其基础研究却很少。我们开发了一种显微照相技术来测量卤代烯丙基在铟表面的反应速率，并描述了用于区分扩散控制和动力学控制的数学模型。测量结果表明该反应是扩散控制的，非均相速率常数的最小值为1×10⁻³ cm s⁻¹。这些结果拓宽了显微术在测量导致固体金属消耗的非均相反应速率方面的适用性。
