Coordination structure and extraction behavior of a silver ion with N-substituted-9-aza-3,6,12,15-tetrathiaheptadecanes: significant effect of Ph-C-N framework on the extractability

Satoshi Iwatsuki; Atsushi Ichiyama; Syogo Tanooka; Mari Toyama; Kosuke Katagiri; Masatoshi Kawahata; Kentaro Yamaguchi; Hiroshi Danjo; Kenji Chayama

doi:10.1039/c6dt01535b

Coordination structure and extraction behavior of a silver ion with N-substituted-9-aza-3,6,12,15-tetrathiaheptadecanes: significant effect of Ph-C-N framework on the extractability

Dalton Trans. 2016 Aug 2;45(31):12548-58. doi: 10.1039/c6dt01535b.

Authors

Satoshi Iwatsuki¹, Atsushi Ichiyama¹, Syogo Tanooka¹, Mari Toyama¹, Kosuke Katagiri¹, Masatoshi Kawahata², Kentaro Yamaguchi², Hiroshi Danjo¹, Kenji Chayama¹

Affiliations

¹ Department of Chemistry, Konan University, 8-9-1 Okamoto, Higashinada, Kobe 658-8501, Japan. [email protected] [email protected].
² Kagawa School of Pharmaceutical Sciences, Tokushima Bunri University, 1314-1 Shido, Sanuki, Kagawa 769-2193, Japan.

PMID: 27435308
DOI: 10.1039/c6dt01535b

Abstract

N-Substituted-9-aza-3,6,12,15-tetrathiaheptadecanes having Ph-C-N frameworks (N-R-ATH; R = benzyl (N-Bn-ATH), 4-nitrobenzyl (N-NO2Bn-ATH), and diphenylmethyl (N-Ph2CH-ATH)) were synthesized, and their Ag(i) complexes were structurally characterized. X-Ray crystal structure analyses of [Ag(N-R-ATH)](BF4) (R = Bn and Ph2CH) revealed monomeric tetra-S-coordinated complex cation structures without the N-coordination, and a benzene ring of the N-R group covered over the amine nitrogen atom. The precise extraction analyses of a Ag(i) ion with ATH derivatives (L = N-R-ATHs and N-H-ATH) associated with the (1)H NMR analyses of the [Ag(L)](+) complexes in polar and non-polar solvents revealed that the introduction of the N-substituent significantly enhanced the extractability of Ag(+), due to the "hydrophobic cover" effect by the Ph-C-N framework in the [Ag(N-R-ATH)](+) complexes.