Kaplanskiy, Mark V. and Karpov, Valerii V. and Tupikina, Elena Yu. and Antonov, Alexander S. (2024) NMR detection of the strained metallacycles in organolithiums: theoretical study. ORGANIC & BIOMOLECULAR CHEMISTRY, 22 (5). pp. 982-989. ISSN 1477-0520, 1477-0539
Full text not available from this repository. (Request a copy)Abstract
For the first time through quantum chemistry methods, the effective use of 1JCLi spin-spin coupling constants as descriptors for assessing the formation of strained metallacycles is demonstrated. Both acyclic organolithiums and 3- to 7-membered metallacycles are examined. 80 organolithium compounds, including both monomeric and dimeric species, with ligands containing fluorine, nitrogen, oxygen, and carbon (in the form of carbanions), are tested. In general, the 1JCLi values below 12 Hz for monomeric species and below 6 Hz for dimeric species serve as clear indicators of strained monomeric metallacycle formation (for 6Li nuclei). The primary contributor to the overall 1JCLi value is the Fermi-contact term, which correlates directly with the carbon-lithium interatomic distance and allows to distinguish between dimers and monomers. The use of 1JCLi spin-spin coupling constants as descriptors of the strained metallacycles is demonstrated through quantum chemistry methods.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | ION-PAIR; REAGENTS; REACTIVITY; LITHIATION |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 12 Mar 2024 11:08 |
| Last Modified: | 04 Mar 2025 09:49 |
| URI: | https://pred.uni-regensburg.de/id/eprint/59425 |
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