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Title: Cyanohydridoborate Anions: Synthesis, Salts, and Low-Viscosity Ionic Liquids

Abstract

High-yield syntheses up to molar scales for salts of [BH(CN) 3] - (2) and [BH 2(CN) 2] - (3) starting from commercially available Na[BH 4] (Na5), Na[BH 3(CN)] (Na4), BCl 3, (CH 3) 3SiCN, and KCN were develop-ed. Direct conversion of Na5 into K2 was accomplished with (CH 3) 3SiCN and (CH 3) 3SiCl as a catalyst in an autoclave. Alternatively, Na5 is converted into Na[BH{OC(O)R} 3] (R = alkyl) that is more reactive towards (CH 3) 3SiCN and thus provides an easy access to salts of 2. Some reaction intermediates were identified, e.g. Na[BH(CN){OC(O)Et} 2] (Na7b) and Na[BH(CN) 2{OC(O)Et}](Na8 b). A third entry to 2 and 3 uses ether adducts of BHCl 2 or BH 2Cl such as the commercial 1,4-dioxane adducts that react with KCN and Me 3SiCN. Alkali metal salts of 2 and 3 are starting materials for various inorganic and organic salts, e.g. low viscosity ionic liquids (ILs). [EMIm]3 is the lowest viscosity and highest conducting non-protic IL known with 10.2 mPa·s and 32.6 mS·cm -1 at 20 °C. The ILs are thermally, chemically, and electrochemically robust. These properties are crucial for applications in electro-chemical devices, e.g. dye-sensitized solar cells (Grätzel cells).

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3];  [4];  [3];  [5]; ORCiD logo [1]
  1. Institut für nachhaltige Chemie &, Katalyse mit Bor (ICB), Institut für Anorganische ChemieJulius-Maximilians-Universität Würzburg Am Hubland 97074 Würzburg Germany
  2. Institut für Organische Chemie &, Center for Nanosystems ChemistryJulius-Maximilians-Universität Würzburg Am Hubland 97074 Würzburg Germany
  3. Physical Sciences DivisionPacific Northwest National Laboratory 902 Battelle Boulevard, P.O. Box 999, MSIN K8-88 Richland WA 99352 USA
  4. Department of ChemistryPurdue University 560 Oval Drive West Lafayette IN 47907 USA
  5. Institut für nachhaltige Chemie &, Katalyse mit Bor (ICB), Institut für Anorganische ChemieJulius-Maximilians-Universität Würzburg Am Hubland 97074 Würzburg Germany; ConsultantMerck KGaA 64293 Darmstadt Germany
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1507130
Report Number(s):
PNNL-SA-137921
Journal ID: ISSN 0947-6539
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 25; Journal Issue: 14; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English

Citation Formats

Bischoff, Lisa A., Drisch, Michael, Kerpen, Christoph, Hennig, Philipp T., Landmann, Johannes, Sprenger, Jan A. P., Bertermann, Rüdiger, Grüne, Matthias, Yuan, Qinqin, Warneke, Jonas, Wang, Xue‐Bin, Ignat'ev, Nikolai V., and Finze, Maik. Cyanohydridoborate Anions: Synthesis, Salts, and Low-Viscosity Ionic Liquids. United States: N. p., 2019. Web. doi:10.1002/chem.201804698.
Bischoff, Lisa A., Drisch, Michael, Kerpen, Christoph, Hennig, Philipp T., Landmann, Johannes, Sprenger, Jan A. P., Bertermann, Rüdiger, Grüne, Matthias, Yuan, Qinqin, Warneke, Jonas, Wang, Xue‐Bin, Ignat'ev, Nikolai V., & Finze, Maik. Cyanohydridoborate Anions: Synthesis, Salts, and Low-Viscosity Ionic Liquids. United States. doi:10.1002/chem.201804698.
Bischoff, Lisa A., Drisch, Michael, Kerpen, Christoph, Hennig, Philipp T., Landmann, Johannes, Sprenger, Jan A. P., Bertermann, Rüdiger, Grüne, Matthias, Yuan, Qinqin, Warneke, Jonas, Wang, Xue‐Bin, Ignat'ev, Nikolai V., and Finze, Maik. Thu . "Cyanohydridoborate Anions: Synthesis, Salts, and Low-Viscosity Ionic Liquids". United States. doi:10.1002/chem.201804698.
@article{osti_1507130,
title = {Cyanohydridoborate Anions: Synthesis, Salts, and Low-Viscosity Ionic Liquids},
author = {Bischoff, Lisa A. and Drisch, Michael and Kerpen, Christoph and Hennig, Philipp T. and Landmann, Johannes and Sprenger, Jan A. P. and Bertermann, Rüdiger and Grüne, Matthias and Yuan, Qinqin and Warneke, Jonas and Wang, Xue‐Bin and Ignat'ev, Nikolai V. and Finze, Maik},
abstractNote = {High-yield syntheses up to molar scales for salts of [BH(CN)3]- (2) and [BH2(CN)2]- (3) starting from commercially available Na[BH4] (Na5), Na[BH3(CN)] (Na4), BCl3, (CH3)3SiCN, and KCN were develop-ed. Direct conversion of Na5 into K2 was accomplished with (CH3)3SiCN and (CH3)3SiCl as a catalyst in an autoclave. Alternatively, Na5 is converted into Na[BH{OC(O)R}3] (R = alkyl) that is more reactive towards (CH3)3SiCN and thus provides an easy access to salts of 2. Some reaction intermediates were identified, e.g. Na[BH(CN){OC(O)Et}2] (Na7b) and Na[BH(CN)2{OC(O)Et}](Na8 b). A third entry to 2 and 3 uses ether adducts of BHCl2 or BH2Cl such as the commercial 1,4-dioxane adducts that react with KCN and Me3SiCN. Alkali metal salts of 2 and 3 are starting materials for various inorganic and organic salts, e.g. low viscosity ionic liquids (ILs). [EMIm]3 is the lowest viscosity and highest conducting non-protic IL known with 10.2 mPa·s and 32.6 mS·cm-1 at 20 °C. The ILs are thermally, chemically, and electrochemically robust. These properties are crucial for applications in electro-chemical devices, e.g. dye-sensitized solar cells (Grätzel cells).},
doi = {10.1002/chem.201804698},
journal = {Chemistry - A European Journal},
issn = {0947-6539},
number = 14,
volume = 25,
place = {United States},
year = {2019},
month = {2}
}

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