Kumar Parveen, Komulainen Joonas, Frontera Antonio, Ward Jas S, Schalley Christoph, Rissanen Kari, Puttreddy Rakesh
Department of chemistry, University of Jyvaskyla, P.O. BOX 35, FI-40014, Jyväskylä, Finland.
Department of Chemistry, Universitat de les Illes Balears, Crta de Valldemossa km 7.5, 07122, Palma de Mallorca, Baleares, Spain.
Chemistry. 2023 Dec 11;29(69):e202302162. doi: 10.1002/chem.202302162. Epub 2023 Oct 26.
Homoleptic [L-I-L] iodine(I) complexes (where L is a R R R N tertiary amine) were synthesized via the [L-Ag-L] → [L-I-L] cation exchange reaction. In solution, the amines form [R R R N-Ag-NR R R ] silver(I) complexes, which crystallize out from solution as the meso-[L-Ag-L] complexes, as characterized by X-ray crystallography. The subsequent [L-I-L] iodine(I) analogues were extremely reactive and could not be isolated in the solid state. Density functional theory (DFT) calculations were performed to study the Ag -N and I -N interaction energies in silver(I) and iodine(I) complexes, with the former ranging from -80 to -100 kJ mol and latter from -260 to -279 kJ mol . The X-ray crystal structures revealed Ag ⋅⋅⋅C and Ag ⋅⋅⋅H-C short contacts between the silver(I) cation and flexible N-alkyl/N-aryl groups, which are the first of their kind in such precursor complexes.
通过[L-Ag-L]→[L-I-L]阳离子交换反应合成了同配体[L-I-L]碘（I）配合物（其中L为RRRN叔胺）。在溶液中，胺形成[RRRN-Ag-NRRR]银（I）配合物，经X射线晶体学表征，其以内消旋-[L-Ag-L]配合物的形式从溶液中结晶析出。随后得到的[L-I-L]碘（I）类似物反应活性极高，无法以固态形式分离出来。进行了密度泛函理论（DFT）计算，以研究银（I）和碘（I）配合物中的Ag-N和I-N相互作用能，前者范围为-80至-100 kJ·mol，后者范围为-260至-279 kJ·mol。X射线晶体结构揭示了银（I）阳离子与柔性N-烷基/N-芳基基团之间的Ag⋅⋅⋅C和Ag⋅⋅⋅H-C短接触，这在这类前体配合物中尚属首次。
