N-heterocyclic carbenes with three and six fluorous ponytails and their highly fluorophilic Rh and Ir complexes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F67985858%3A_____%2F23%3A00569339" target="_blank" >RIV/67985858:_____/23:00569339 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/44555601:13440/23:43897612

Výsledek na webu

<a href="https://hdl.handle.net/11104/0340756" target="_blank" >https://hdl.handle.net/11104/0340756</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.jorganchem.2022.122605" target="_blank" >10.1016/j.jorganchem.2022.122605</a>

Jazyk výsledku

angličtina

Název v původním jazyce

N-heterocyclic carbenes with three and six fluorous ponytails and their highly fluorophilic Rh and Ir complexes

Popis výsledku v původním jazyce

Reactions of 1-methylimidazole and 1-(1-methylethyl)imidazole with (3-iodopropyl)tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane gave the corresponding 1-alkyl-3-(3-(tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) silyl) propyl) imidazolium iodides 1 and 2. Reaction of imidazole in excess with (3-iodopropyl)tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane afforded 1-(3-(tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) silyl) propyl) imidazole 3 which was further reacted with (3-iodopropyl)tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane to produce the doubly tagged 1,3-bis[3-(tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) silyl) propyl] imidazolium iodide 4 and by anion exchange a tetrafluoroborate salt 5. The prepared imidazolium iodides 1,2, and 4 were then used as pre-cursors in synthesis of chlorido(cycloocta-1,5-diene)rhodium or-iridium complexes bearing Nheterocyclic carbenes with one 3-[tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silyl]propyl-substituent and methyl-, 1-methylethyl-and another 3-[ tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl )silyl]propyl-substituent on nitrogens, 6 11. The metal complexes were equimolar mixtures of conformational enantiomers as was best documented by the 1H NMR signals of diastereotopic CH2 protons next to nitrogen. Fluorophilicity fi as the natural logarithm of partition coefficient Pi between fluorous and organic phase of the complexes was determined in the standard solvent system (perfluoro)methylcyclohexane/toluene. All the complexes are fluorophilic with variation of fi between 0.96 and 4.06, the complexes with high values may be classified as highly fluorophilic (heavy fluorous).(c) 2022 Elsevier B.V. All rights reserved.

Název v anglickém jazyce

N-heterocyclic carbenes with three and six fluorous ponytails and their highly fluorophilic Rh and Ir complexes

Popis výsledku anglicky

Reactions of 1-methylimidazole and 1-(1-methylethyl)imidazole with (3-iodopropyl)tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane gave the corresponding 1-alkyl-3-(3-(tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) silyl) propyl) imidazolium iodides 1 and 2. Reaction of imidazole in excess with (3-iodopropyl)tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane afforded 1-(3-(tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) silyl) propyl) imidazole 3 which was further reacted with (3-iodopropyl)tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane to produce the doubly tagged 1,3-bis[3-(tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) silyl) propyl] imidazolium iodide 4 and by anion exchange a tetrafluoroborate salt 5. The prepared imidazolium iodides 1,2, and 4 were then used as pre-cursors in synthesis of chlorido(cycloocta-1,5-diene)rhodium or-iridium complexes bearing Nheterocyclic carbenes with one 3-[tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silyl]propyl-substituent and methyl-, 1-methylethyl-and another 3-[ tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl )silyl]propyl-substituent on nitrogens, 6 11. The metal complexes were equimolar mixtures of conformational enantiomers as was best documented by the 1H NMR signals of diastereotopic CH2 protons next to nitrogen. Fluorophilicity fi as the natural logarithm of partition coefficient Pi between fluorous and organic phase of the complexes was determined in the standard solvent system (perfluoro)methylcyclohexane/toluene. All the complexes are fluorophilic with variation of fi between 0.96 and 4.06, the complexes with high values may be classified as highly fluorophilic (heavy fluorous).(c) 2022 Elsevier B.V. All rights reserved.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

Journal of Organometallic Chemistry

ISSN

0022-328X

e-ISSN

1872-8561

Svazek periodika

986

Číslo periodika v rámci svazku

FEB 15

Stát vydavatele periodika

CH - Švýcarská konfederace

Počet stran výsledku

9

Strana od-do

122605

Kód UT WoS článku

000915633600001

EID výsledku v databázi Scopus

2-s2.0-85145830029