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

Result description

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.

Keywords

magnetic-resonance-spectroscopystructural-characterizationmonocarbaborane chemistry

The result's identifiers

Alternative languages

  • Result language

    angličtina

  • Original language name

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

  • Original language description

    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.

  • Czech name

  • Czech description

Classification

  • Type

    Jx - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

  • CEP classification

    CA - Inorganic chemistry

  • OECD FORD branch

Result continuities

Others

  • Publication year

    2016

  • Confidentiality

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

Data specific for result type

  • Name of the periodical

    Inorganic Chemistry

  • ISSN

    0020-1669

  • e-ISSN

  • Volume of the periodical

    55

  • Issue of the periodical within the volume

    17

  • Country of publishing house

    US - UNITED STATES

  • Number of pages

    5

  • Pages from-to

    8839-8843

  • UT code for WoS article

    000382713900070

  • EID of the result in the Scopus database

    2-s2.0-84986184237

Basic information

Result type

Jx - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

Jx

CEP

CA - Inorganic chemistry

Year of implementation

2016