Unique reactivity of an alpha-ketiminopyridine ligand with metal-alkyls: Synthesis and ROP of epsilon-caprolactone

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F21%3A39917683" target="_blank" >RIV/00216275:25310/21:39917683 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlelanding/2021/nj/d0nj05498d" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2021/nj/d0nj05498d</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d0nj05498d" target="_blank" >10.1039/d0nj05498d</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Unique reactivity of an alpha-ketiminopyridine ligand with metal-alkyls: Synthesis and ROP of epsilon-caprolactone

Popis výsledku v původním jazyce

The reaction of an alpha-ketimininopyridine ligand 2-((Me)C = N(C6H3-2,6-iPr(2)))-6-(OMe)C5H3N (L-1) with metal-alkyls, such as MeLi, Et2Zn, Me3Al and Me2AlCl, was studied. The reaction of L-1 with MeLi led exclusively to the formation of [2-((H2C)C-N(C6H3-2,6-iPr(2)))-6-(OMe)C5H3N]Li center dot(THF)(2) (1 center dot(THF)(2)) with a deprotonated ketimine methyl group as a product of methane elimination. The treatment of L-1 with Et2Zn provided, at the first stage, only complex [2-((Me)C = N(C6H3-2,6-iPr(2)))-6-(OMe)C5H3N]ZnEt2 (2). The nonstability of 2 led to ethane elimination along with the deprotonation of a ketimine methyl group, which further yielded [2-((H2C)C-N(C6H3-2,6-iPr(2)))-6-(OMe)C5H3N]ZnEt (3). In contrast, Me3Al reacted with L-1 in a carboalumination fashion and [2-((Me)(2)C-N(C6H3-2,6-iPr(2)))-6-(OMe)C5H3N]AlMe2 (4) was isolated. In the case of Me2AlCl, an ionic species {[2-((Me)C = N(C6H3-2,6-iPr(2)))-6-(OMe)C5H3N]AlMe2}(+) {Me2AlCl2}(-) (5) was formed as a result of a spontaneous dissociation of Me2AlCl initiated by the ligand L-1. Since compounds 2-5 contain a metal-alkyl fragment, they were used as pre-catalysts in ROP of epsilon-caprolactone, as well as compound 1 center dot(THF)(2).

Název v anglickém jazyce

Unique reactivity of an alpha-ketiminopyridine ligand with metal-alkyls: Synthesis and ROP of epsilon-caprolactone

Popis výsledku anglicky

The reaction of an alpha-ketimininopyridine ligand 2-((Me)C = N(C6H3-2,6-iPr(2)))-6-(OMe)C5H3N (L-1) with metal-alkyls, such as MeLi, Et2Zn, Me3Al and Me2AlCl, was studied. The reaction of L-1 with MeLi led exclusively to the formation of [2-((H2C)C-N(C6H3-2,6-iPr(2)))-6-(OMe)C5H3N]Li center dot(THF)(2) (1 center dot(THF)(2)) with a deprotonated ketimine methyl group as a product of methane elimination. The treatment of L-1 with Et2Zn provided, at the first stage, only complex [2-((Me)C = N(C6H3-2,6-iPr(2)))-6-(OMe)C5H3N]ZnEt2 (2). The nonstability of 2 led to ethane elimination along with the deprotonation of a ketimine methyl group, which further yielded [2-((H2C)C-N(C6H3-2,6-iPr(2)))-6-(OMe)C5H3N]ZnEt (3). In contrast, Me3Al reacted with L-1 in a carboalumination fashion and [2-((Me)(2)C-N(C6H3-2,6-iPr(2)))-6-(OMe)C5H3N]AlMe2 (4) was isolated. In the case of Me2AlCl, an ionic species {[2-((Me)C = N(C6H3-2,6-iPr(2)))-6-(OMe)C5H3N]AlMe2}(+) {Me2AlCl2}(-) (5) was formed as a result of a spontaneous dissociation of Me2AlCl initiated by the ligand L-1. Since compounds 2-5 contain a metal-alkyl fragment, they were used as pre-catalysts in ROP of epsilon-caprolactone, as well as compound 1 center dot(THF)(2).

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/GA20-10417S" target="_blank" >GA20-10417S: Auto-ionizované kationty nepřechodných prvků jako katalyzátory ROP reakcí</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2021

Kód důvěrnosti údajů

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

Název periodika

New Journal of Chemistry

ISSN

1144-0546

e-ISSN

—

Svazek periodika

45

Číslo periodika v rámci svazku

8

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

9

Strana od-do

3800-3808

Kód UT WoS článku

000623596600006

EID výsledku v databázi Scopus

2-s2.0-85101854908