Racemization Pathway for MoO2(acac)2Favored over Ray-Dutt, Bailar, and Conte-Hippler Twists

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Chiral cis-MoO2(acac)2racemizes via four pathways that agree with and extend upon Muetterties' topological analysis for dynamic MX2(chel)2complexes. Textbook Ray-Dutt and Bailar twists are the least favored with barriers of 27.5 and 28.7 kcal/mol, respectively. Rotating both acac ligands of the Bailar structure by 90° gives the lower Conte-Hippler twist (20.0 kcal/mol), which represents a valley-ridge inflection that invokes the trans isomer. The most favorable is a new twist that was found by 90° rotation of only one acac ligand of the Bailar structure. The gas-phase barrier of 17.4 kcal/mol for this Dhimba-Muller-Lammertsma twist further decreases upon inclusion of the effects of solvents to 16.3 kcal/mol (benzene), 16.2 kcal/mol (toluene), and 15.4 kcal/mol (chloroform), which are in excellent agreement with the reported experimental values.

Original languageEnglish
Pages (from-to)14918-14923
Number of pages6
JournalInorganic Chemistry
Issue number38
Publication statusPublished - 26 Sept 2022

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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