Linear bis‐Coordinate Silver(I) and Iodine(I) Complexes with R3R2R1N Tertiary Amines

Abstract

AbstractHomoleptic [L−I−L]+ iodine(I) complexes (where L is a R3R2R1N tertiary amine) were synthesized via the [L−Ag−L]+→ [L−I−L]+ cation exchange reaction. In solution, the amines form [R3R2R1N−Ag−NR1R2R3]+ 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−1 and latter from −260 to −279 kJ mol−1. The X‐ray crystal structures revealed Ag+⋅⋅⋅Cπ 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.