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A “nucleophilic” iodine in a halogen-bonded iodonium complex manifests an unprecedented I+···Ag+ interaction
Chem ( IF 19.1 ) Pub Date : 2021-02-08 , DOI: 10.1016/j.chempr.2021.01.003
Shilin Yu , Parveen Kumar , Jas S. Ward , Antonio Frontera , Kari Rissanen

When an electron is removed from a halogen atom, it forms a halenium ion X+ (X = I, Br, Cl). In halogen bonding (XB), X+ is considered as a strong XB donor, and when interacting with two XB acceptors (e.g., pyridine), it forms a halonium XB complex with a [N–I–N] three-center-four-electron bond with the two XB acceptors. An unprecedented I+···Ag+ interaction occurs between a [L1–I–L1]+ halogen-bonded complex and a [L2–Ag–L2]+ complex in which the iodonium ion acts like a nucleophile and donates electrons to the silver(I) cation. The X-ray diffraction analysis reveals a short contact [3.4608(3) Å] between the I+ and Ag+ cations, and ITC measurements give a ΔG of −6.321 kcal/mol and Ka∼37,000 M−1 for the 1:1 complex. The DFT computational study on the nature of the I+···Ag+ interaction indicates that the I+ is nucleophilic in character, manifesting an unusual and strongly attractive interaction between the I+ and Ag+ cations.



中文翻译:

卤素键合的碘鎓络合物中的“亲核”碘表现出前所未有的I + ···Ag +相互作用

当电子从卤原子上除去时,它形成a离子X +(X = I,Br,Cl)。在卤素键(XB)中,X +被认为是强大的XB供体,当与两个XB受体(例如吡啶)相互作用时,它会形成具有[N–I–N]三中心四的ha XB配合物。与两个XB受体的电子键。[L 1 –I–L 1 ] +卤素键复合物与[L 2 –Ag–L 2 ] +之间发生前所未有的I + ··Ag +相互作用碘鎓离子的作用类似于亲核试剂,并向银(I)阳离子提供电子。X射线衍射分析显示I +和Ag +阳离子之间有短接触[3.4608(3)Å] ,ITC测量得出1:的ΔG为-6.321 kcal / mol,K a约为37,000 M -1。 1个复合体。DFT对I + ···Ag +相互作用性质的计算研究表明,I +具有亲核性质,表现出I +与Ag +阳离子之间异常且强烈的相互作用。

更新日期:2021-04-08
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