Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland.
J Org Chem. 2010 Aug 6;75(15):4944-9. doi: 10.1021/jo100399g.
In this paper we investigate the influence of intramolecular noncovalent interaction, i.e., H-bonding and Li-bonding, on the properties of substituents communicating through the resonance (mesomeric) effect in such molecular systems as salicylaldehyde, o-hydroxy Schiff base, o-nitrosophenol, and their lithium analogues. The investigated systems are usually considered as molecular patterns of intramolecular resonance-assisted hydrogen bonds (or its analogues in the case of Li-bonded systems). We show that the relation between intramolecular noncovalent interactions, A-H...B and A-Li...B, and the pi-electron delocalization in the sequence of pi-conjugated covalent bonds linking A and B can be considered in terms of the Hammett-like substituent effect in which electron-donating and electron-withdrawing properties of substituents are affected by the noncovalent interaction.
本文研究了分子内非共价相互作用（即氢键和锂离子键）对通过共振（离域）效应相互作用的取代基性质的影响，研究对象为水杨醛、邻羟基席夫碱、邻硝基苯酚及其锂类似物等分子体系。这些被研究的体系通常被认为是分子内共振辅助氢键的分子模式（或者在锂离子键合体系的情况下是其类似物）。我们表明，可以根据哈米特型取代基效应来考虑分子内非共价相互作用 A-H…B 和 A-Li…B 与连接 A 和 B 的π共轭共价键中的π电子离域之间的关系，其中取代基的供电子和吸电子性质受到非共价相互作用的影响。
