Facile activation of alkynes with a boraguanidinato-stabilized germylene: a combined experimental and theoretical study

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F17%3A39911691" target="_blank" >RIV/00216275:25310/17:39911691 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11310/17:10363766

Výsledek na webu

<a href="http://dx.doi.org/10.1039/c7dt01950e" target="_blank" >http://dx.doi.org/10.1039/c7dt01950e</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c7dt01950e" target="_blank" >10.1039/c7dt01950e</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Facile activation of alkynes with a boraguanidinato-stabilized germylene: a combined experimental and theoretical study

Popis výsledku v původním jazyce

A boraguanidinato-stabilized germylene, [(i-Pr)(2)NB(N-2,6-Me2C6H3)2] Ge, reacts with alkynes RC CR selectively in a 2 : 1 molar ratio to afford 3,4-R, R&apos;-1,2-digermacyclobut-3-enes 1a-e as the products of formal [2 + 2 + 2] cyclization [R/R&apos; = Me/Me (1a), Ph/Ph (1b), Ph/H (1c), t-Bu/H (1d) and Cy/H (1e)]. Ferrocenyl-substituted alkynes react similarly, yielding the corresponding ferrocenylated 3,4-R, R&apos;-1,2-digermacyclobut-3-enes 2a-d [where R/R&apos; = Fc/H (2a), Fc/Me (2b), Fc/Ph (2c), and Fc/Fc (2d); Fc = ferrocenyl]. By contrast, only one of the triple bonds available in conjugated diynes RC CC CR is activated with the germylene, while the second one remains intact even in the presence of an excess of the germylene. The exclusive formation of 3,4-R,(C CR)-1,2-digermacyclobut-3-enes 3a-c [R = Ph (3a), t-Bu(3b), and Fc (3c)] was ascribed to a steric repulsion around the second triple bond. On the other hand, the reaction of the germylene with more flexible dialkyne fc(CuCPh)(2) (fc = ferrocene-1,1&apos;-diyl) proceeded in the expected manner, producing compound 4, where both triple bonds are transformed into 1,2-digermacyclobut- 3-ene rings by reaction with four equivalents of the germylene. All compounds were characterized by multinuclear NMR spectroscopy, Raman and IR spectroscopy, and in the case of 1a-c, 2a, 2c, 3a, 3b and 4, also by single-crystal X-ray diffraction analysis. The ferrocenyl substituted compounds were studied by cyclic voltammetry (CV). Finally, the plausible reaction pathway was studied for a model reaction of [(i-Pr)(2)NB(N-2,6-Me2C6H3)(2)] Ge with MeC CMe using DFT computations.

Název v anglickém jazyce

Facile activation of alkynes with a boraguanidinato-stabilized germylene: a combined experimental and theoretical study

Popis výsledku anglicky

A boraguanidinato-stabilized germylene, [(i-Pr)(2)NB(N-2,6-Me2C6H3)2] Ge, reacts with alkynes RC CR selectively in a 2 : 1 molar ratio to afford 3,4-R, R&apos;-1,2-digermacyclobut-3-enes 1a-e as the products of formal [2 + 2 + 2] cyclization [R/R&apos; = Me/Me (1a), Ph/Ph (1b), Ph/H (1c), t-Bu/H (1d) and Cy/H (1e)]. Ferrocenyl-substituted alkynes react similarly, yielding the corresponding ferrocenylated 3,4-R, R&apos;-1,2-digermacyclobut-3-enes 2a-d [where R/R&apos; = Fc/H (2a), Fc/Me (2b), Fc/Ph (2c), and Fc/Fc (2d); Fc = ferrocenyl]. By contrast, only one of the triple bonds available in conjugated diynes RC CC CR is activated with the germylene, while the second one remains intact even in the presence of an excess of the germylene. The exclusive formation of 3,4-R,(C CR)-1,2-digermacyclobut-3-enes 3a-c [R = Ph (3a), t-Bu(3b), and Fc (3c)] was ascribed to a steric repulsion around the second triple bond. On the other hand, the reaction of the germylene with more flexible dialkyne fc(CuCPh)(2) (fc = ferrocene-1,1&apos;-diyl) proceeded in the expected manner, producing compound 4, where both triple bonds are transformed into 1,2-digermacyclobut- 3-ene rings by reaction with four equivalents of the germylene. All compounds were characterized by multinuclear NMR spectroscopy, Raman and IR spectroscopy, and in the case of 1a-c, 2a, 2c, 3a, 3b and 4, also by single-crystal X-ray diffraction analysis. The ferrocenyl substituted compounds were studied by cyclic voltammetry (CV). Finally, the plausible reaction pathway was studied for a model reaction of [(i-Pr)(2)NB(N-2,6-Me2C6H3)(2)] Ge with MeC CMe using DFT computations.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

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OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/GA17-10377S" target="_blank" >GA17-10377S: Multideprotonovatelné, ambifilické a hybridní ligandy s uspořádáním vhodným pro tvorbu oligometalických komplexů kovů</a><br>

Návaznosti

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

Rok uplatnění

2017

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

—

Svazek periodika

46

Číslo periodika v rámci svazku

36

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

15

Strana od-do

12339-12353

Kód UT WoS článku

000411224500040

EID výsledku v databázi Scopus

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