摘要：

This chapter discusses recent computational studies of radical cations in the context of qualitative concepts of classical physical organic chemistry. It demonstrates how such basic concepts, such as conjugation and electronic state or even more fundamental notions of structure, bonding, and mechanism, lead to new and interesting effects in radical cation chemistry that are quite different than what is usually expected in the chemistry of neutral compounds. The chapter also discusses how these effects need to be taken into consideration to understand the chemistry of radical cations. It concentrates on computational results from the laboratory, and discusses experimental data only in the context of the calculational data. The differences in structure and reactivity between neutral, closed-shell organic compounds and their radical cation counterparts as well as the generally low activation energies indicate the potential for developing new synthetic methodology or to uncover biochemical reaction mechanisms that use electron transfer catalysis.

展开