Optically-active tris(O,O′-dialkyl dithiophosphato-S,S′)chromium(III) complexes. Isolation of diastereoisomers and isomerization reactions

Hiromi Ohta, Masakazu Kita, Hideaki Kanno, Masaaki Kojima

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Two optically-active O,O′-dialkyl dithiophosphate ligands, (Bor)2PS2- and (Men)2PS2-, were prepared from P2S5 and the monoterpene alcohols, D-borneol and L-menthol. The chromium(III) complexes, [Cr{(Bor)2PS2}3] and [Cr{(Men)2PS2}3], were prepared by reaction with Cr(NO3)3·9H2O in acetone. The diastereoisomers (Δ and Λ) were separated by fractional crystallization of the complexes from toluene ([Cr{(Bor)2PS2}3]) or acetone ([Cr{(Men)2PS2}3]). The (-)680/CD-Δ-[Cr{(Bor)2 PS2}3] isomer was obtained from the less soluble part. This isomer shows extremely strong CD, Δε (680 nm, toluene) = -15.0 M-1 cm-1. The Δ-[Cr{(Men)2PS2}3] isomer could not be obtained in the optically-pure state, since the complex inverts appreciably during the recrystallization procedure. Activation parameters for isomerization (epimerization), Δ→Λ and Λ→Δ were determined for both complexes, [Cr{(Bor)2PS2}3] and [Cr{(Men)2PS2}3]. [Cr{(Men)2PS2}3] isomerizes much faster than [Cr{(Bor)2PS2}3].

Original languageEnglish
Pages (from-to)75-79
Number of pages5
JournalInorganica Chimica Acta
Volume311
Issue number1-2
DOIs
Publication statusPublished - Dec 22 2000
Externally publishedYes

Keywords

  • Chromium complexes
  • Diastereoisomers
  • Dithiophosphato complexes
  • Isomerization
  • Optically-active complexes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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