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pH‐Controlled Multiple Chiral Inversion That Induces Molecular Dimerization in a Gold(I)–Cobalt(III) Coordination System with L‐Cysteinate
Authors:Pei‐Shan Lee  Dr. Asako Igashira‐Kamiyama  Dr. Naoto Kuwamura  Dr. Nobuto Yoshinari  Prof. Takumi Konno
Affiliation:1. Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560‐0043 (Japan);2. JST‐CREST, Toyonaka, Osaka 560‐0043 (Japan)
Abstract:Herein, a unique coordination system that exhibits multiple chiral inversions and molecular dimerization in response to a subtle pH change is reported. Treatment of (Δ)2‐H3[Au3Co2(L ‐cys)6] (H3[ 1 a ]) with [Co3(aet)6](NO3)3 (aet=2‐aminoethanethiolate) in water at pH 7 gave a 1:1 complex salt of [Co3(aet)6]3+ and [ 1 a ]3?, retaining the AuI3CoIII2 structure and chiral configurations of [ 1 a ]3?. Similar treatment at pH 9 led to not only the inversion of all of the chiral CoIII and S centers but also the dimerization of [ 1 a ]3?, giving a 2:1 complex salt of [Co3(aet)6]3+ and (Λ)4(R)12‐[Au6Co4(L ‐cys)12]6? ([ 2 ]6?). When dissociated from [Co3(aet)6]3+ in solution, [ 2 ]6? was converted to (Λ)2(R)6‐[Au3Co2(L ‐cys)6]3? ([ 1 b ]3?) with retention of the chiral configurations.
Keywords:amino acids  chirality  gold  heterometallic complexes  S ligands
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