Construction of Bimetallic and Trimetallic Aggregates with a [Y(COT)2]- Building Block : Solid-State Structures and Solution Behavior
© 2025 The Authors. Published by American Chemical Society.
| Publié dans: | Organometallics. - 1998. - 44(2025), 18 vom: 22. Sept., Seite 2092-2098 |
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| Auteur principal: | |
| Autres auteurs: | , , |
| Format: | Article en ligne |
| Langue: | English |
| Publié: |
2025
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| Accès à la collection: | Organometallics |
| Sujets: | Journal Article |
| Résumé: | © 2025 The Authors. Published by American Chemical Society. Several new bimetallic and trimetallic complexes containing the [Y-(COT)2]- unit in different coordination environments are synthesized and fully characterized using X-ray crystallography and NMR spectroscopy. These complexes include [K([2.2.2]-cryptand)]-[Y-(COT)2] (1), [K-(18-crown-6)-(THF)]-[Y-(COT)2] (2), [Y2K2(COT)4(THF)4] (3), and [YKCa-(COT)3(THF)3] (4). In the presence of secondary ligands, bimetallic ionic pairs that comprise a [Y-(COT)2]- sandwich and a solvent-wrapped K+ ion are formed in 1 and 2. In contrast, 3 represents a bimetallic tetradecker oligomer with two [Y-(COT)2]- units bridged by a K+ ion and a terminal [K-(THF)4]+ moiety. Complex 4 is a heterotrimetallic triple-decker with an axial arrangement of three metal centers to form [Y-(COT)2K-(COT)-Ca-(THF)3]. Structural analysis shows the Y-COTcentroid distances in the [Y-(COT)2]- sandwich are equidistant (1.884(6) Å) in 1 but become asymmetric in 2-4 (1.857(3)-1.952(3) Å), reflecting additional external coordination. The two COT rings are parallel in 1 and become increasingly tilted from 0.8 to 27.5° in 2-4, respectively. Multinuclear NMR spectroscopy measurements reveal the solution behavior of the sandwich and heterometallic multidecker COT-based products. The observed NMR spectroscopic trends corroborate with weak interactions between the [Y-(COT)2]- unit and cationic moieties persisting in solutions of 2-4 |
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| Description: | Date Revised 28.09.2025 published: Electronic-eCollection Citation Status PubMed-not-MEDLINE |
| ISSN: | 0276-7333 |
| DOI: | 10.1021/acs.organomet.5c00233 |