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Linear bis-Coordinate Silver(I) and Iodine(I) Complexes with R3R2R1N Tertiary Amines
P. Kumar, J. Komulainen, A. Frontera, J.S. Ward, C.A. Schalley, K. Rissanen, R. Puttreddy – 2023
Homoleptic [L–I–L]+ iodine(I) complexes (where L = prochiral NR1R2R3 tertiary amine) were synthesized via the [L–Ag–L]+ → [L–I–L]+ cation exchange reaction. In solution, the pseudo-enantiomorphic amines form a “locked” iodine(I) complex, [R1R2R3N-I-NR1R2R3]+, where the two prochiral amines became become chiral with opposite absolute configurations of the sp3-nitrogen forming meso-[L–I–L]+ halogen(I) complexes. Unlike the [L–Ag–L]+ silver(I) precursor complexes with meso-configuration, characterized by single crystal X-ray crystallography, the corresponding iodine(I) analogues are not stable in solid-state due the their high reactivity. Density functional theory (DFT) calculations are used to compute the Ag+–N and I+–N bond energies, and to study the Cπ···I+ and C–H···I+ interactions between the N-alkyl and N-aryl groups and the iodine(I) cation expected to stabilize these complexes.
Linear bis-Coordinate Silver(I) and Iodine(I) Complexes with R3R2R1N Tertiary Amines