Acta Phys. -Chim. Sin. ›› 2018, Vol. 34 ›› Issue (5): 497-502.doi: 10.3866/PKU.WHXB201709222

Special Issue: Special issue for Chemical Concepts from Density Functional Theory

• ARTICLE • Previous Articles     Next Articles

Application of Natural Orbital Fukui Functions and Bonding Reactivity Descriptor in Understanding Bond Formation Mechanisms Underlying [2+4] and [4+2] Cycloadditions of o-Thioquinones with 1, 3-Dienes

Chaoxian YAN,Fan YANG,Ruizhi WU,Dagang ZHOU,Xing YANG,Panpan ZHOU*()   

  • Received:2017-08-30 Published:2018-01-24
  • Contact: Panpan ZHOU
  • Supported by:
    the National Natural Science Foundation of China(21403097);the Fundamental Research Funds for the Central Universities, China(lzujbky-2016-45)


o-Thioquinones can undergo either [2+4] or [4+2] cycloaddition reactions with acyclic dienes. To illustrate the bonding processes in these cycloadditions, the natural orbital Fukui function (NOFF) and bonding reactivity descriptor have been employed. The electrophilicity of a bond or an orbital in the o-thioquinone as well as in the acyclic diene has been found using the NOFF, which suggests that electron transfer takes place from an electron-donating bonding orbital to an electron-accepting antibonding/bonding orbital, leading to the cyclic product via the formation of a circular loop and two covalent bonds. The bonding reactivity descriptor shows that covalent bonds readily form between atom k1 of one molecule with a large fk1+ value and atom k2 of another molecule with a large fk2- value. Both the NOFF and the bonding reactivity descriptor are efficient tools for interpreting the mechanism underlying the [2+4] and [4+2] cycloaddition between o-thioquinones and acyclic dienes.

Key words: Fukui function, Natural orbital Fukui function (NOFF), Bonding reactivity descriptor, Cycloaddition, Nucleophilic/electrophilic attack