Department of Chemistry, University of Oxford Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA, UK.
Chemistry. 2022 Dec 1;28(67):e202201838. doi: 10.1002/chem.202201838. Epub 2022 Oct 11.
The synthesis and characterisation of a library of acyclic antimony(III) and bismuth(III) triaryl pnictogen bonding (PnB) receptor systems are reported. In the first-generation receptor series, quantitative H NMR chloride titration experiments in THF solvent media reveal halide anion binding potency is intimately correlated with both the electronic-withdrawing nature of the aryl- substituent and the polarisability of the PnB donor. Further extensive anion binding investigations with the most potent Sb- and Bi-based PnB receptors: 1⋅Sb and 1⋅Bi , reveal novel selectivity profiles, both displaying Cl selectivity relative to the heavier halides and, impressively, to a range of highly basic oxoanions. The synthesis and preliminary chloride anion binding studies of a series of novel tripodal tris-proto-triazole triaryl Sb(III) and Bi(III) mixed PnB-HB receptor systems are also described. Whereas parent triphenyl Sb(III) and Bi(III) compounds are incapable of binding Cl in THF solvent media, the PnB-triazole HB host systems exhibit notable halide affinity.
报道了一系列非循环三芳基膦键（PnB）受体的锑（III）和铋（III）配合物的合成和表征。在第一代受体系列中，在 THF 溶剂介质中进行的定量 H-NMR 氯化物滴定实验表明，卤化物阴离子的结合能力与芳基取代基的电子受主性质和 PnB 供体的极化率密切相关。对最有效基于 Sb 和 Bi 的 PnB 受体 1⋅Sb 和 1⋅Bi 进行了进一步广泛的阴离子结合研究，揭示了新颖的选择性特征，它们均表现出相对于较重卤化物以及令人印象深刻的一系列高碱性氧代阴离子的 Cl 选择性。还描述了一系列新型三脚架三原均三唑三芳基 Sb(III)和 Bi(III)混合 PnB-HB 受体系统的合成和初步氯化物阴离子结合研究。尽管母体三苯基 Sb(III)和 Bi(III)化合物在 THF 溶剂介质中不能结合 Cl，但 PnB-三唑 HB 主体系统表现出显著的卤化物亲和力。
