Electronic Structure Analysis and Reactivity of the Bimetallic Bis-Titanocene Vinylcarboxylate Complex, [(Cp2Ti)2(O2C3TMS2)]†
Multimetallic redox cooperativity features heavily in both bioinorganic and synthetic reactions. Here, the electronic structure of the bimetallic Ti/Ti complex 11, [(Cp2Ti)2(O2C3TMS2)] has been revisited with EPR, confirming a predominantly TiIII/TiIII electronic structure. Reactions of 11 with 2,6-...
| Publié dans: | Polyhedron. - 1997. - 207(2021) vom: 01. Okt. |
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| Auteur principal: | |
| Autres auteurs: | , , , , |
| Format: | Article en ligne |
| Langue: | English |
| Publié: |
2021
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| Accès à la collection: | Polyhedron |
| Sujets: | Journal Article |
| Résumé: | Multimetallic redox cooperativity features heavily in both bioinorganic and synthetic reactions. Here, the electronic structure of the bimetallic Ti/Ti complex 11, [(Cp2Ti)2(O2C3TMS2)] has been revisited with EPR, confirming a predominantly TiIII/TiIII electronic structure. Reactions of 11 with 2,6-dimethylphenyl isocyanide (CNXyl), TMSCl, MeI, and BnCl were explored, revealing differential redox chemistry of the bimetallic core. In reactions with CNXyl and TMSCl, the metallacyclic TiIII center remained unperturbed, with reactions taking place at the pendent κ2(O,O)-titanocene fragment, while reaction with MeI resulted in remote oxidation of the metallacyclic Ti center, indicative of a cooperative redox process. All structures were studied via X-ray diffraction and EPR spectroscopic analysis, and their electronic structures are discussed in the context of the covalent bond classification (CBC) electron counting method |
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| Description: | Date Revised 30.11.2021 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 0277-5387 |
| DOI: | 10.1016/j.poly.2021.115368 |