Abstract
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 language | English |
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Pages (from-to) | 14918-14923 |
Number of pages | 6 |
Journal | Inorganic Chemistry |
Volume | 61 |
Issue number | 38 |
DOIs | |
Publication status | Published - 26 Sept 2022 |
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry