Activation barrier, symmetry

Thermal dimerization of ethylene to cyclobutane is forbidden by orbital symmetry (Sect 3.5 in Chapter Elements of a Chemical Orbital Theory by Inagaki in this volume). The activation barrier is high E =44 kcal mof ) [9]. Cyclobutane cannot be prepared on a preparative scale by the dimerization of ethylenes despite a favorable reaction enthalpy (AH = -19 kcal mol" ). Thermal reactions between alkenes usually proceed via diradical intermediates [10-12]. The process of the diradical formation is the most favored by the HOMO-LUMO interaction (Scheme 25b in chapter Elements of a Chemical Orbital Theory ). The intervention of the diradical intermediates impfies loss of stereochemical integrity. This is a characteric feature of the thermal reactions between alkenes in the delocalization band of the mechanistic spectrum. 

Cnm is the quantum average of proton coupling, and AG m is the activation barrier for n — m transition. With explicit computation of Cnm, and considering reaction symmetry within the Q mode, a new term, Ea = h2(y2/2inu, whose physical interpretation is the coupling term between Q mode and solvent polarity, is introduced, accompanied by removal of the summation term in (13) ... 

Molecular Motions and Dynamic Structures. Molecular motions are of quite general occurrence in the solid state for molecules of high symmetry (22,23). If the motion does not introduce disorder into the crystal lattice (as, for example, the in-plane reorientation of benzene which occurs by 60° jumps between equivalent sites) it is not detected by diffraction measurements which will find a seemingly static lattice. Such molecular motions may be detected by wide-line proton NMR spectroscopy and quantified by relaxation-time measurements which yield activation barriers for the reorientation process. In addition, in some cases, the molecular reorientation may be coupled with a chemical exchange process as, for example, in the case of many fluxional organometallic molecules. ... 

As far as the definition of a as a measure of the symmetry of the activation barrier is concerned, as shown in Figure 15, let us focus on the apical region of the intersection between the free energy curves illustrated in Figure 14. 

The other major reaction pathway for oxonium ylide is [l,2]-shift (Stevens rearrangement). Compared with [2,3]-sigmatropic rearrangement, which is an orbital symmetry-allowed concerted process, the [l,2]-shift has higher activation barrier, [1,2]-Shift is generally considered as stepwise process with radical pair as possible intermediates. 

Fig. 30 Energy diagram showing the major configurations that contribute to any cycloaddition reaction, DA, D+A, and 3D 3A. For allowed reactions, DA and D+A mix, thereby lowering the activation barrier. For forbidden reactions, mixing of DA and D+A is precluded by symmetry...

If die products are lower in energy than file reactants in a reaction step, file symmetry of file activation barrier causes file transition to lie less than halfway along the reaction coordinate (Figure 5.8). The structure of the activated complex is more closely related to the structure of file reactants than to the structure of fire products. 

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