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Title: Rational design of an argon-binding superelectrophilic anion

Chemically binding to argon (Ar) at room temperature has remained the privilege of the most reactive electrophiles, all of which are cationic (or even dicationic) in nature. Herein, we report a concept for the rational design of anionic superelectrophiles that are composed of a strong electrophilic center firmly embedded in a negatively charged framework of exceptional stability. To validate our concept, we synthesized the percyano-dodecoborate [B 12 (CN) 12 ] 2− , the electronically most stable dianion ever investigated experimentally. It serves as a precursor for the generation of the monoanion [B 12 (CN) 11 ] , which indeed spontaneously binds Ar at 298 K. Our mass spectrometric and spectroscopic studies are accompanied by high-level computational investigations including a bonding analysis of the exceptional B-Ar bond. The detection and characterization of this highly reactive, structurally stable anionic superelectrophile starts another chapter in the metal-free activation of particularly inert compounds and elements.
Authors:
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Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
OSTI Identifier:
1505256

Mayer, Martin, van Lessen, Valentin, Rohdenburg, Markus, Hou, Gao-Lei, Yang, Zheng, Exner, Rüdiger M., Aprà, Edoardo, Azov, Vladimir A., Grabowsky, Simon, Xantheas, Sotiris S., Asmis, Knut R., Wang, Xue-Bin, Jenne, Carsten, and Warneke, Jonas. Rational design of an argon-binding superelectrophilic anion. United States: N. p., Web. doi:10.1073/pnas.1820812116.
Mayer, Martin, van Lessen, Valentin, Rohdenburg, Markus, Hou, Gao-Lei, Yang, Zheng, Exner, Rüdiger M., Aprà, Edoardo, Azov, Vladimir A., Grabowsky, Simon, Xantheas, Sotiris S., Asmis, Knut R., Wang, Xue-Bin, Jenne, Carsten, & Warneke, Jonas. Rational design of an argon-binding superelectrophilic anion. United States. doi:10.1073/pnas.1820812116.
Mayer, Martin, van Lessen, Valentin, Rohdenburg, Markus, Hou, Gao-Lei, Yang, Zheng, Exner, Rüdiger M., Aprà, Edoardo, Azov, Vladimir A., Grabowsky, Simon, Xantheas, Sotiris S., Asmis, Knut R., Wang, Xue-Bin, Jenne, Carsten, and Warneke, Jonas. 2019. "Rational design of an argon-binding superelectrophilic anion". United States. doi:10.1073/pnas.1820812116.
@article{osti_1505256,
title = {Rational design of an argon-binding superelectrophilic anion},
author = {Mayer, Martin and van Lessen, Valentin and Rohdenburg, Markus and Hou, Gao-Lei and Yang, Zheng and Exner, Rüdiger M. and Aprà, Edoardo and Azov, Vladimir A. and Grabowsky, Simon and Xantheas, Sotiris S. and Asmis, Knut R. and Wang, Xue-Bin and Jenne, Carsten and Warneke, Jonas},
abstractNote = {Chemically binding to argon (Ar) at room temperature has remained the privilege of the most reactive electrophiles, all of which are cationic (or even dicationic) in nature. Herein, we report a concept for the rational design of anionic superelectrophiles that are composed of a strong electrophilic center firmly embedded in a negatively charged framework of exceptional stability. To validate our concept, we synthesized the percyano-dodecoborate [B 12 (CN) 12 ] 2− , the electronically most stable dianion ever investigated experimentally. It serves as a precursor for the generation of the monoanion [B 12 (CN) 11 ] − , which indeed spontaneously binds Ar at 298 K. Our mass spectrometric and spectroscopic studies are accompanied by high-level computational investigations including a bonding analysis of the exceptional B-Ar bond. The detection and characterization of this highly reactive, structurally stable anionic superelectrophile starts another chapter in the metal-free activation of particularly inert compounds and elements.},
doi = {10.1073/pnas.1820812116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {4}
}

Works referenced in this record:

Chemistry with ADF
journal, January 2001
  • te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.
  • Journal of Computational Chemistry, Vol. 22, Issue 9, p. 931-967
  • DOI: 10.1002/jcc.1056