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Title: Rational design of an argon-binding superelectrophilic anion

Abstract

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:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1505256
Alternate Identifier(s):
OSTI ID: 1528932
Grant/Contract Number:  
AC02-05CH11231
Resource 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 Volume: 116 Journal Issue: 17; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; superelectrophilic anions; multiple-charged anions; Ar compounds; photoelectron spectroscopy; dodecaborates

Citation Formats

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., 2019. 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. Fri . "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 = 17,
volume = 116,
place = {United States},
year = {2019},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1073/pnas.1820812116

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Cited by: 6 works
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    Works referencing / citing this record:

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