Is the Single-Transition-State Model Appropriate for the Fundamental Reactions of Organic Chemistry? Experimental Methods and Data Treatment, Pertinent Reactions, and Complementary Computational Studies

摘要: Abstract The experimental recording of spectrophotometric data suitable for detailed kinetic analysis and reaction mechanism determination is covered early in the chapter with examples experiments subsequent treatment on a variety different chemical systems. Several new methods to distinguish between single-step complex mechanisms are described detail. fundamental organic reactions more detail were limited recent work four general types. These include (1) proton transfer nitroalkanes related compounds, (2) S N 2 CH 3 -X where X leaving group, (3) electrophilic aromatic substitution, (4) hydride NADH/NAD + model In all cases possible, discussion studies was complemented by computational same involved short-lived intermediates could only from single transition state. Computational confirmed nature provided structures likely reactions. energies noncovalently bonded highly dependent method therefore not confirm apparent Gibbs free states.