{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Dhimba G"],"funding":["National Research Foundation"],"pagination":["14918-14923"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC9516665"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["61(38)"],"pubmed_abstract":["Chiral <i>cis</i>-MoO<sub>2</sub>(acac)<sub>2</sub> racemizes via four pathways that agree with and extend upon Muetterties' topological analysis for dynamic MX<sub>2</sub>(chel)<sub>2</sub> complexes. 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 (tolu"],"journal":["Inorganic chemistry"],"pubmed_title":["Racemization Pathway for MoO<sub>2</sub>(acac)<sub>2</sub> Favored over Ray-Dutt, Bailar, and Conte-Hippler Twists."],"pmcid":["PMC9516665"],"funding_grant_id":["120842"],"pubmed_authors":["Lammertsma K","Muller A","Dhimba G"],"additional_accession":[]},"is_claimable":false,"name":"Racemization Pathway for MoO<sub>2</sub>(acac)<sub>2</sub> Favored over Ray-Dutt, Bailar, and Conte-Hippler Twists.","description":"Chiral <i>cis</i>-MoO<sub>2</sub>(acac)<sub>2</sub> racemizes via four pathways that agree with and extend upon Muetterties' topological analysis for dynamic MX<sub>2</sub>(chel)<sub>2</sub> complexes. 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 (tolu","dates":{"release":"2022-01-01T00:00:00Z","publication":"2022 Sep","modification":"2025-04-19T05:18:10.515Z","creation":"2025-04-19T05:18:10.515Z"},"accession":"S-EPMC9516665","cross_references":{"pubmed":["35980189"],"doi":["10.1021/acs.inorgchem.2c00824"]}}