Number of the records: 1
Synthetic routes to carbon substituted cobalt bis(dicarbollide) alkyl halides and aromatic amines along with closely related irregular pathways
- 1.
SYSNO ASEP 0584541 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Synthetic routes to carbon substituted cobalt bis(dicarbollide) alkyl halides and aromatic amines along with closely related irregular pathways Author(s) Nekvinda, Jan (UACH-T) RID, SAI, ORCID
Bavol, Dmytro (UACH-T) SAI, RID, ORCID
Litecká, Miroslava (UACH-T) ORCID, SAI, RID
Tüzün, Ece Zeynep (UACH-T) ORCID, RID, SAI
Dušek, Michal (FZU-D) RID, ORCID, SAI
Grüner, Bohumír (UACH-T) RID, SAI, ORCIDNumber of authors 6 Source Title Dalton Transactions. - : Royal Society of Chemistry - ISSN 1477-9226
Roč. 53, č. 13 (2024), s. 5816-5826Number of pages 11 s. Language eng - English Country GB - United Kingdom Subject RIV CA - Inorganic Chemistry OECD category Inorganic and nuclear chemistry R&D Projects GA21-14409S GA ČR - Czech Science Foundation (CSF) LM2023051 GA MŠMT - Ministry of Education, Youth and Sports (MEYS) Method of publishing Open access Institutional support UACH-T - RVO:61388980 ; FZU-D - RVO:68378271 UT WOS 001182046700001 EID SCOPUS 85187671114 DOI 10.1039/d4dt00072b Annotation Carbon substituted cobalt bis(dicarbollide) alkyl halides [(1-X-(CH2)n-1,2-C2B9H10)(1,2-C2B9H11)-3,3′-Co]Me4N (X = Br, I, n = 1-3) are prepared in high yields (>90%) from their corresponding alcohols without side skeletal substitutions. These species offer access to the synthesis of aromatic cobalt bis(dicarbollide) amines, however only for particular terminal halogen substitution, the propylene pendant arm, and under appropriately controlled reaction conditions. Thus, the compounds substituted at cage carbon atoms with a propylene linker and terminal aromatic amine groups could be prepared. In other cases, numerous irregular reaction pathways occur, undoubtedly as a consequence of the bulky anionic boron cage in close proximity to the reaction site. Among them, an unusual intramolecular hydroboration forming rigidified carbon-to-boron bridged isomeric anions with an asymmetric structure that correspond to formulae [(1,8′-μ-C2H4)-(1,2-C2B9H10)(1′,2′-C2B9H10)-3,3′-Co]− and [(1,7′-μ-C2H4)-(1,2-C2B9H10)(1′,2′-C2B9H10)-3,3′-Co]− is described herein and the former isomer is structurally characterized. This product with a restrained geometry is widely accessible through nucleophile and/or thermally induced decomposition of (pseudo)halides attached to the cage via an ethylene linker. Surprisingly enough, also doubly bridged isomeric species [(1,8-μ-C2H4-1,2-C2B9H9)2-3,3′-Co]− and [(1,7-μ-C2H4-1,2-C2B9H9)2-3,3′-Co]− are available in good yield using these methods. Furthermore, other more typical side reactions are discussed, i.e. nucleophilic reactions of propyl halides with Me3N formed apparently by disproportionation of Me4N+ at higher temperatures or with pyridine used as a base. Workplace Institute of Inorganic Chemistry Contact Jana Kroneislová, krone@iic.cas.cz, Tel.: 311 236 931 Year of Publishing 2025 Electronic address https://hdl.handle.net/11104/0352638
Number of the records: 1