Click Dehydrogenation of Carbon-Substituted nido-5,6-C2B8H12 Carboranes: A General Route to closo-1,2-C2B8H10 Derivatives

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388980%3A_____%2F16%3A00463696" target="_blank" >RIV/61388980:_____/16:00463696 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216275:25310/16:39901649

Výsledek na webu

<a href="http://dx.doi.org/10.1021/acs.inorgchem.6b01386" target="_blank" >http://dx.doi.org/10.1021/acs.inorgchem.6b01386</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.inorgchem.6b01386" target="_blank" >10.1021/acs.inorgchem.6b01386</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Click Dehydrogenation of Carbon-Substituted nido-5,6-C2B8H12 Carboranes: A General Route to closo-1,2-C2B8H10 Derivatives

Popis výsledku v původním jazyce

Triethylamine-catalyzed dehydrogenation of carbon-disubstituted dicarbaboranes 5,6-R-2-nido-5,6-C2B8H10 [1, where R = H (1a), Me (1b), and Ph (1c)] in refluxing acetonitrile leads to a high-yield (up to 85-95%) formation of a series of dicarbaboranes 1,2-R-2-closo-1,2-C2B8H8 (2). The monosubstituted 6-R-nido-5,6-C2B8H11 (3) analogues [where R = Ph (3a), naph (1-naphthyl; 3b), Bu (3c)] afforded 1-R-1,2-closo C2B8H9 (4) isomers [where R = Ph (4a), naph (4b), n-Bu (4c)] as the main products; compounds 4a and 4c were accompanied by 2-R-1;2-C2B8H9 (5) isomers (total yields up to 90%), with the 4/5 molar ratio being strongly dependent on the nature of R (4:1 and 1:1, respectively). All of these cage-closure reactions are supposed to proceed via the stage of the corresponding Et3NH+ salts of nido anions [5,6-R-2-5,6-C2B8H9](-) (1(-)) and [6-R-5,6-C2B8H10](-) (3(-)), which lose H-2 and Et3N upon heating (dehydrodeamination). The cage-closure mechanisms leading to closo isomers 2, 4, and 5 have been substantiated by B3LYP/6-31+G* calculations of the reaction profile for a simple 1a(-) -> 2a + H- conversion. All of the compounds isolated have been characterized by multinuclear (B-11, H-1, and C-13) NMR spectroscopy, mass spectrometry, and elemental analyses, and the structure of 1-Ph-closo-1,2-C2B8H9 (4a) was established by an X-ray diffraction study.

Název v anglickém jazyce

Click Dehydrogenation of Carbon-Substituted nido-5,6-C2B8H12 Carboranes: A General Route to closo-1,2-C2B8H10 Derivatives

Popis výsledku anglicky

Triethylamine-catalyzed dehydrogenation of carbon-disubstituted dicarbaboranes 5,6-R-2-nido-5,6-C2B8H10 [1, where R = H (1a), Me (1b), and Ph (1c)] in refluxing acetonitrile leads to a high-yield (up to 85-95%) formation of a series of dicarbaboranes 1,2-R-2-closo-1,2-C2B8H8 (2). The monosubstituted 6-R-nido-5,6-C2B8H11 (3) analogues [where R = Ph (3a), naph (1-naphthyl; 3b), Bu (3c)] afforded 1-R-1,2-closo C2B8H9 (4) isomers [where R = Ph (4a), naph (4b), n-Bu (4c)] as the main products; compounds 4a and 4c were accompanied by 2-R-1;2-C2B8H9 (5) isomers (total yields up to 90%), with the 4/5 molar ratio being strongly dependent on the nature of R (4:1 and 1:1, respectively). All of these cage-closure reactions are supposed to proceed via the stage of the corresponding Et3NH+ salts of nido anions [5,6-R-2-5,6-C2B8H9](-) (1(-)) and [6-R-5,6-C2B8H10](-) (3(-)), which lose H-2 and Et3N upon heating (dehydrodeamination). The cage-closure mechanisms leading to closo isomers 2, 4, and 5 have been substantiated by B3LYP/6-31+G* calculations of the reaction profile for a simple 1a(-) -> 2a + H- conversion. All of the compounds isolated have been characterized by multinuclear (B-11, H-1, and C-13) NMR spectroscopy, mass spectrometry, and elemental analyses, and the structure of 1-Ph-closo-1,2-C2B8H9 (4a) was established by an X-ray diffraction study.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CA - Anorganická chemie

OECD FORD obor

—

Projekt

<a href="/cs/project/GA16-01618S" target="_blank" >GA16-01618S: Desetivrcholové dikarbaboranové molekulární útvary vytvořené alkylací</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2016

Kód důvěrnosti údajů

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

Název periodika

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

—

Svazek periodika

55

Číslo periodika v rámci svazku

17

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

5

Strana od-do

8839-8843

Kód UT WoS článku

000382713900070

EID výsledku v databázi Scopus

2-s2.0-84986184237