Chalcogen Bonding in Solution: Interactions of Benzotelluradiazoles with Anionic and Uncharged Lewis Bases
Chalcogen Bonding in Solution: Interactions of Benzotelluradiazoles with Anionic and Uncharged Lewis Bases
复制标题
DOI：
10.1021/ja512183e
复制
发表时间：
2015-04-01
影响因子：
15
通讯作者：
Taylor, Mark S.
中科院分区：
文献类型：
--
作者：
Garrett, Graham E.;Gibson, Gregory L.;Taylor, Mark S.
硫属元素键合是缺电子、共价键合的硫属元素（Te、Se、S）与刘易斯碱之间的非共价相互作用。虽然大量的证据支持存在的硫属元素键合在固态，定量数据的相互作用的强度在溶液中的阶段是缺乏的。本文报道了苯并碲二唑与各种刘易斯碱（Cl-、Br-、I-、NO3-和奎宁环）在有机溶剂中的缔合常数的测定。通过UV-vis、H-1和F-19 NMR光谱以及nano-ESI质谱研究了苯并碲二唑在硫族元素成键相互作用中的参与。从这些数据中可以明显看出，硫属元素键的自由能在供体、受体和溶剂变化时的趋势，包括硫属元素键供体能力与碲中心处的计算静电势之间的线性自由能关系。使用色散校正的B 97-D3泛函的计算结果与实验的硫族键合自由能吻合得很好。
Chalcogen bonding is the noncovalent interaction between an electron-deficient, covalently bonded chalcogen (Te, Se, S) and a Lewis base. Although substantial evidence supports the existence of chalcogen bonding in the solid state, quantitative data regarding the strengths of the interactions in the solution phase are lacking. Herein, determinations of the association constants of benzotelluradiazoles with a variety of Lewis bases (Cl-, Br-, I-, NO3- and quinuclidine, in organic solvent) are described. The participation of the benzotelluradiazoles in chalcogen bonding interactions was probed by UV-vis, H-1 and F-19 NMR spectroscopy as well as nano-ESI mass spectrometry. Trends in the free energy of chalcogen bonds upon variation of the donor, acceptor and solvent are evident from these data, including a linear free energy relationship between chalcogen bond donor ability and calculated electrostatic potential at the tellurium center. Calculations using the dispersion-corrected B97-D3 functional were found to give good agreement with the experimental free energies of chalcogen bonding.