Chiral-at-Metal Racemization Unraveled for MX2(a-chel)2 by means of a Computational Analysis of MoO2(acnac)2

Research output: Contribution to journalArticlepeer-review


Octahedral chiral-at-metal complexes MX2(a-chel)2 (a-chel=asymmetric chelate) can rearrange their ligands by four mechanisms known as the Bailar (B), Ray-Dutt (RD), Conte-Hippler (CH), and Dhimba-Muller-Lammertsma (DML) twists. Racemization involves their interconnections, which were computed for MoO2(acnac)2 (acnac=β-ketoiminate) using density functional theory at ωB97x-D with the 6-31G(d,p) and 6-311G(2d,p) basis sets and LANL2DZ for molybdenum. Racemizing the cis(NN) isomer, being the global energy minimum with trans oriented imine groups, is a three step process (DML-CH-DML) that requires 17.4 kcal/mol, while all three cis isomers (cis(NN), cis(NO), and cis(OO)) interconvert at ≤17.9 kcal/mol. The B and RD twists are energetically not competitive and neither are the trans isomers. The interconnection of all enantiomeric minima and transition structures is summarized in a graph that also visualizes valley ridge inflection points for two of the three CH twists. Geometrical features of the minima and twists are given. Lastly, the influence of N-substitution on the favored racemization pathway is evaluated. The present comprehensive study serves as a template for designing chiral-at-metal MX2(a-chel)2 catalysts that may retain their chiral integrity.

Original languageEnglish
Article numbere202302516
JournalChemistry - A European Journal
Issue number66
Publication statusPublished - 24 Nov 2023


  • N,O-ligands
  • coordination modes
  • density functional calculations
  • homogeneous catalysis
  • molybdenum

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Organic Chemistry


Dive into the research topics of 'Chiral-at-Metal Racemization Unraveled for MX2(a-chel)2 by means of a Computational Analysis of MoO2(acnac)2'. Together they form a unique fingerprint.

Cite this