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

Result code in 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>

Alternative codes found

RIV/00216208:11310/17:10363766

Result on the web

<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>

Result language

angličtina

Original language name

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

Original language description

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.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

10402 - Inorganic and nuclear chemistry

Project

<a href="/en/project/GA17-10377S" target="_blank" >GA17-10377S: Multideprotonable, ambiphilic and hybrid ligands with appropriate shape and electron pool for formation of oligometallic complexes</a><br>

Continuities

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

Publication year

2017

Confidentiality

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

Name of the periodical

Dalton Transactions

ISSN

1477-9226

e-ISSN

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Volume of the periodical

46

Issue of the periodical within the volume

36

Country of publishing house

GB - UNITED KINGDOM

Number of pages

15

Pages from-to

12339-12353

UT code for WoS article

000411224500040

EID of the result in the Scopus database

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