1. Racemic Tartrate/Malate Anions Combine with Racemic Complex Cations to Form Optically Active Ionic Crystals.
- Author
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Uno, Masashi, Kojima, Tatsuhiro, Kuwamura, Naoto, Yoshinari, Nobuto, and Konno, Takumi
- Subjects
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IONIC crystals , *OPTICAL resolution , *ANIONS , *JOB performance , *CHEMICAL species , *RACEMIC mixtures - Abstract
Spontaneous resolution has attracted continuing attention in various research fields since Pasteur's work on the crystallization behavior of racemic tartrate. Here, a unique example of this phenomenon is reported, involving ionic crystals generated from racemic RR/SS‐ tartrate or R/S‐malate and racemic ΔΔ/ΛΛ‐[Ag3Rh2(2‐aminoethanethiolato)6]3+ (ΔΔ/ΛΛ‐[1]3+) in water. RR‐ and SS‐tartrate selectively recognize the ΛΛ and ΔΔ isomers of [1]3+ to produce ionic crystals of (ΛΛ‐[1])2(RR‐tartrate)3 and (ΔΔ‐[1])2(SS‐tartrate)3, respectively, which can undergo spontaneous resolution. While spontaneous resolution also occurs when using R/S‐malate, R‐ and S‐malate select the opposite isomers of [1]3+ to give ionic crystals of (ΔΔ‐[1])2(R‐malate)3 and (ΛΛ‐[1])2(S‐malate)3, respectively. In the presence of S‐aspartate, (ΛΛ‐[1])2(R‐tartrate)3 and (ΔΔ‐[1])2(S‐tartrate)3 are preferentially crystallized from ΔΔ/ΛΛ‐[1]3+ and RR/SS‐tartrate at solution pH values of 6 and 10, respectively. This finding provides significant insight into the optical resolution of chemical species by spontaneous resolution and the origin of homochirality in nature. [ABSTRACT FROM AUTHOR]
- Published
- 2021
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