A theoretical study on the metal cation-pi complexes of Zn2 and Cd2 with benzene and cyclohexene

作者：Li Zhen Hua; Liu Jianliang; Qiao Minghua; Fan Kang Nian^*

来源：Molecular Physics, 2009, 107(8-12): 1271-1282.

DOI：10.1080/00268970902926220

• metal cation-pi complex
• DFT
• benzene
• cyclohexene

Transition metal cation-pi complexes of Zn2 and Cd2 with benzene and cyclohexene have been studied with density functional B3PW91 method. Natural bond orbital (NBO) analyses on the direct cation-pi complexes ( with direct pi-ion contact) indicate that the interaction between the pi orbital of the pi systems and the empty valance s orbital of the cation (pi(PI) -> s(M2 ) interactions) dominates the cation-pi interactions. Energetical results indicate that formation of metal cation-pi complexes in the gas phase is always energetically favourable and these complexes can thus be prepared and observed in experiments in the gas phase. However, in aqueous solution the desolvation penalty of Zn2 and Cd2 is so high that it is energetically unfavourable to form metal cation-pi complexes from hydrated Zn2 and Cd2 at both 0 K and room temperature. It would thus be predicted that metal cation-pi complexes of Zn2 and Cd2 are not likely to be observed in aqueous solution.

• 出版日期2009
• 单位复旦大学