Chiral-at-Molybdenum – A Computational Study on N-Substituted cis-MoO2(nacnac)2

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Cis-MoO2(nacnac)2 (nacnac=β-diketiminate) can be a viable chiral-at-metal catalyst when its two β-diketiminate (nacnac) ligands are N-substituted to prevent Λ⇌Δ racemization. Even simple methyl groups raise the barriers for racemization significantly for the Bailar, Rây-Dutt, Conte-Hippler, and Dhimba-Muller-Lammertsma (DML) twists to a respectable 28.5, 37.8, 30.5, and 25.1 kcal/mol, respectively, at ωB97X-D/6-311+G(2d,p) (LANL2DZ for Mo) including acetonitrile solvation. The lowest energy DML barrier increases to ΔGo=27.4 kcal/mol with N-substituted t-butyl groups. The nacnac ligands’ electronic and steric components to the racemization barriers are discussed.

Original languageEnglish
Article numbere202300256
JournalEuropean Journal of Inorganic Chemistry
Issue number25
Publication statusPublished - 1 Sept 2023


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

ASJC Scopus subject areas

  • Inorganic Chemistry


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