Synthetic routes to carbon substituted cobalt bis(dicarbollide) alkyl halides and aromatic amines along with closely related irregular pathways

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F68378271%3A_____%2F24%3A00584541" target="_blank" >RIV/68378271:_____/24:00584541 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388980:_____/24:00584541

Výsledek na webu

<a href="https://hdl.handle.net/11104/0352638" target="_blank" >https://hdl.handle.net/11104/0352638</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d4dt00072b" target="_blank" >10.1039/d4dt00072b</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Synthetic routes to carbon substituted cobalt bis(dicarbollide) alkyl halides and aromatic amines along with closely related irregular pathways

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Synthetic routes to carbon substituted cobalt bis(dicarbollide) alkyl halides and aromatic amines along with closely related irregular pathways

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10302 - Condensed matter physics (including formerly solid state physics, supercond.)

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Dalton Transactions

ISSN

1477-9226

e-ISSN

1477-9234

Svazek periodika

53

Číslo periodika v rámci svazku

13

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

11

Strana od-do

5816-5826

Kód UT WoS článku

001182046700001

EID výsledku v databázi Scopus

2-s2.0-85187671114