Devore Daniel P, Ellington Thomas L, Shuford Kevin L
Department of Chemistry and Biochemistry, Baylor University, One Bear Place 97348, Waco, TX, 76798-7348, USA.
Present address: Department of Chemistry, Southern Methodist University, P.O. Box 750314, Dallas, TX 75205, USA.
Chemphyschem. 2024 Dec 16;25(24):e202400607. doi: 10.1002/cphc.202400607. Epub 2024 Nov 3.
Throughout the halogen bonding literature, electron withdrawing groups are relied upon heavily for tuning the interaction strength between the halogen bond donor and acceptor; however, the interplay of electronic effects associated with various substituents is less of a focus. This work utilizes computational techniques to study the degree of σ- and π-electron donating/accepting character of electron withdrawing groups in a prescribed set of halo-alkyne, halo-benzene, and halo-ethynyl benzene halogen bond donors. We examine how these factors affect the σ-hole magnitude of the donors as well as the binding strength of the corresponding complexes with an ammonia acceptor. Statistical analyses aid the interpretation of how these substituents influence the properties of the halogen bond donors and complexes, and show that the electron withdrawing groups that are both σ- and π-electron accepting form the strongest halogen bond complexes.
在整个卤键化学文献中，吸电子基团在调节卤键供体与受体之间的相互作用强度方面起着重要作用；然而，与各种取代基相关的电子效应之间的相互作用却较少受到关注。这项工作利用计算技术研究了一组规定的卤代炔烃、卤代苯和卤代乙炔基苯卤键供体中吸电子基团的σ电子和π电子给体/受体特性程度。我们研究了这些因素如何影响供体的σ空穴大小以及相应配合物与氨受体的结合强度。统计分析有助于解释这些取代基如何影响卤键供体和配合物的性质，并表明既是σ电子受体又是π电子受体的吸电子基团形成最强的卤键配合物。
