Theoretical evidence of persistent chirality in D3 homoleptic hexacoordinate complexes with monodentate ligands

Pere Alemany*, Santiago Alvarez, David Avnir

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

14 Scopus citations

Abstract

A theoretical study of the enantiomer interconversion pathway relevant to racemization reactions of hexacoordinate transition-metal complexes is presented based on density functional calculations. The potential energy surface for the trigonal twist pathway of the [Zr(SH)6]2- model compound has been explored. The optimum structure reproduces, to a very good approximation, the experimental geometry of the analogous compound in which the thiolato groups have C6H4-4-OMe substituents instead of H atoms. A barrier of about 19 kcal mol-1 is estimated for the racemization of [Zr(SH)6]2- and exploratory calculations for [Zr(SC6H4-4-OMe)6]2- indicate that a larger barrier should be expected. For the chiral homoleptic organometallic complexes [ZrMe6]2- and [RhMe6]3- no significant racemization barrier is expected.

Original languageEnglish
Pages (from-to)1952-1957
Number of pages6
JournalChemistry - A European Journal
Volume9
Issue number9
DOIs
StatePublished - 9 May 2003

Keywords

  • Bailar twist
  • Chirality
  • Coordination chemistry
  • Density functional calculations

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