Faculty for Chemistry and Pharmacy - Group of Prof. Zipse

Additional Material, Comments and Corrections to Chapter 2:
"Reactivity Models in Organic Chemistry"

In the second chapter we use transition state theory as a semi-quantitative model for organic reactivity phenomena and explore its relation to potential energy surfaces and simple reaction rate equations. This is followed by the presentation of more specific reactivity concepts such as the Bell-Evans-Polanyi principle, Marcus theory, the HSAB principle, Hammett correlations, the Mayr-Patz equation, and FMO theory. A short comment on solvent effects is also included. The following additional material is available for this chapter:

Additional material for Figure 2.1:
Figure 2.1 displays the potential energy surface (PES) for the reaction of chlorine radical with methane calculated at the (U)M06-2X/cc-pVTZ level of theory. Reaction energies for this system are shown in Figure 2.4.

Additional material for Figure 2.25:
Figure 2.25 shows selected molecular orbitals for pyrrole.

Additional material for Figure 2.26:
Figure 2.26 shows selected molecular orbitals for ethylene and acrylonitrile.

Additional material for Figure 2.27:
Figure 2.27 displays LUMO energy levels for selected carbonyl compounds.

Additional material for Figure 2.29:
Figure 2.29 as well as the modified text addresses the dissociation energy of the sodium chloride ion pair into (a) the respective sodium and chlorine radicals (homolytic dissociation) or (b) the constituent sodium cation and chloride anion (heterolytic dissociation).