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Chromatographic separation was attempted by eluting iridium(III) complexes on a high-performance liquid chromatography (HPLC) column packed with an ion-exchange adduct of synthetic hectorite and -tris(1,10-phenanthroline)ruthenium(II). Affinity was adjusted by altering the loading of Δ-[Ru(phen)₃]²⁺ in the hectorite. Seven kinds of neutral iridium(III) complexes were resolved, with two peaks assigned to the Δ- and Λ- enantiomers. Three kinds of positively charged iridium(III) complexes were eluted, yielding Δ-enantiomers with optical purities of 60%−72% as less strongly adsorbed isomers. The opposite enantiomers were too firmly adsorbed for elution. When a five-coordinated iridium(III) complex (trans-[Ir(iPrBQ)₂Cl]) (iPrBQ = mono-deprotonated 2-isopropylbenzo[h]quinoline), was injected, the entire complex was adsorbed and could not be eluted. Adding a negatively charged chelating ligand (disodium salt of 4,7-diphenylphenanthroline disulfate, Na₂BPS) eluted a negatively charged six-coordinated complex (trans-[Ir(iPrBQ)₂BPS]). The transformation from Δ- or Λ-trans-[Ir(iPrBQ)₂Cl] to trans-[Ir(iPrBQ)₂BPS]− occurred in the column. Notably, the eluted complex exclusively took the Δ-conformation from their ECD spectra. This is the first example of the stereoselective transformation of a coordinatively robust iridium(III) complex by passing it through a short column of 1 cm in length. The column uniquely afforded enantiomerically neutral, positively and negatively charged iridium(III) complexes.

権利情報:

• In Copyright
  

  This is a pre-copyedited, author-produced version of an article accepted for publication in Bulletin of the Chemical Society of Japan following peer review. The version of record Akihiko Yamagishi, Kazuyoshi Takimoto, Kyaw Naing, Kenji Tamura, Masumi Kamon, Jun Yoshida, Hisako Sato, Clay column chromatography for optical resolution: separation and asymmetric induction of cyclometalated iridium(III) complexes, Bulletin of the Chemical Society of Japan, Volume 98, Issue 11, November 2025, uoaf110 is available online at: https://doi.org/10.1093/bulcsj/uoaf110.

キーワード: five-coordinated iridium(III) complexes, stereoselective transformation, vibrational circular dichroism spectroscopy

刊行年月日: 2025-10-29

出版者: Oxford University Press (OUP)

掲載誌:

• Bulletin of the Chemical Society of Japan (ISSN: 00092673) vol. 98 issue. 11 uoaf110

研究助成金:

• KAKENHI JP17H03044
• KAKENHI JP20K21090
• KAKENHI JP22H02033
• KAKENHI JP23K23301
• KAKENHI JP23K13766
• KAKENHI JP23K04783

原稿種別: 著者最終稿 (Accepted manuscript)

MDR DOI: https://doi.org/10.48505/nims.6068

公開URL: https://doi.org/10.1093/bulcsj/uoaf110

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更新時刻: 2026-04-30 12:01:11 +0900

MDRでの公開時刻: 2026-11-04 08:31:57 +0900