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

Abstract

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 ] (Na 5 ), Na[BH 3 (CN)] (Na 4 ), BCl 3 , (CH 3 ) 3 SiCN, and KCN were developed. Direct conversion of Na 5 into K 2 was accomplished with (CH 3 ) 3 SiCN and (CH 3 ) 3 SiCl as a catalyst in an autoclave. Alternatively, Na 5 is converted into Na[BH{OC(O) R } 3 ] ( R =alkyl) that is more reactive towards (CH 3 ) 3 SiCN and thus provides an easy access to salts of 2 . Some reaction intermediates were identified, for example, Na[BH(CN){OC(O)Et} 2 ] (Na 7 b ) and Na[BH(CN) 2 {OC(O)Et}] (Na 8 b ). A third entry to 2 and 3 uses ether adducts of BHCl 2 or BH 2 Cl such as the commercial 1,4‐dioxane adducts that react with KCN and (CH 3 ) 3 SiCN. Alkali metal salts of 2 and 3 are convenient starting materials for organic salts, especially for low viscosity ionic liquids (ILs). [EMIm] 3 has the lowest viscosity and highestmore » conductivity with 10.2 mPa s and 32.6 mS cm −1 at 20 °C known for non‐protic ILs. The ILs are thermally, chemically, and electrochemically robust. These properties are crucial for applications in electrochemical devices, for example, dye‐sensitized solar cells (Grätzel cells).« less

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 Chemie Julius-Maximilians-Universität Würzburg Am Hubland 97074 Würzburg Germany
  2. Institut für Organische Chemie &, Center for Nanosystems Chemistry Julius-Maximilians-Universität Würzburg Am Hubland 97074 Würzburg Germany
  3. Physical Sciences Division Pacific Northwest National Laboratory 902 Battelle Boulevard, P.O. Box 999, MSIN K8-88 Richland WA 99352 USA
  4. Department of Chemistry Purdue University 560 Oval Drive West Lafayette IN 47907 USA
  5. Institut für nachhaltige Chemie &, Katalyse mit Bor (ICB), Institut für Anorganische Chemie Julius-Maximilians-Universität Würzburg Am Hubland 97074 Würzburg Germany, Consultant Merck KGaA 64293 Darmstadt Germany
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1494206
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Name: Chemistry - A European Journal Journal Volume: 25 Journal Issue: 14; Journal ID: ISSN 0947-6539
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
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. Germany: 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. Germany. https://doi.org/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. Mon . "Cyanohydridoborate Anions: Synthesis, Salts, and Low‐Viscosity Ionic Liquids". Germany. https://doi.org/10.1002/chem.201804698.
@article{osti_1494206,
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 = {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 ] (Na 5 ), Na[BH 3 (CN)] (Na 4 ), BCl 3 , (CH 3 ) 3 SiCN, and KCN were developed. Direct conversion of Na 5 into K 2 was accomplished with (CH 3 ) 3 SiCN and (CH 3 ) 3 SiCl as a catalyst in an autoclave. Alternatively, Na 5 is converted into Na[BH{OC(O) R } 3 ] ( R =alkyl) that is more reactive towards (CH 3 ) 3 SiCN and thus provides an easy access to salts of 2 . Some reaction intermediates were identified, for example, Na[BH(CN){OC(O)Et} 2 ] (Na 7 b ) and Na[BH(CN) 2 {OC(O)Et}] (Na 8 b ). A third entry to 2 and 3 uses ether adducts of BHCl 2 or BH 2 Cl such as the commercial 1,4‐dioxane adducts that react with KCN and (CH 3 ) 3 SiCN. Alkali metal salts of 2 and 3 are convenient starting materials for organic salts, especially for low viscosity ionic liquids (ILs). [EMIm] 3 has the lowest viscosity and highest conductivity with 10.2 mPa s and 32.6 mS cm −1 at 20 °C known for non‐protic ILs. The ILs are thermally, chemically, and electrochemically robust. These properties are crucial for applications in electrochemical devices, for example, dye‐sensitized solar cells (Grätzel cells).},
doi = {10.1002/chem.201804698},
journal = {Chemistry - A European Journal},
number = 14,
volume = 25,
place = {Germany},
year = {Mon Feb 11 00:00:00 EST 2019},
month = {Mon Feb 11 00:00:00 EST 2019}
}

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