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Title: Rational design of an argon-binding superelectrophilic anion

Abstract

Chemically binding 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 comprise a strong electrophilic center firmly embedded in a negativelycharged framework of exceptional stability. To validate our concept, we synthesized the percyano-dodecoborate [B12(CN)12]2-, the electronically most stable dianion ever investigated experimentally. It serves as a precursor for the generation of the monoanion [B12(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 first detection and characterization of this highly reactive, structurally stable anionic superelectrophile starts a new chapter in the metal-free activation of particularly inert compounds and elements.

Authors:
 [1];  [2];  [3]; ORCiD logo [4];  [5];  [2]; ORCiD logo [5];  [6];  [7]; ORCiD logo [5];  [1]; ORCiD logo [5];  [2];  [4]
  1. Universitat Leipzig
  2. Bergische Universitat Wuppertal
  3. Universitat Bremen
  4. UNIVERSITY PROGRAMS
  5. BATTELLE (PACIFIC NW LAB)
  6. Universiteit van die Vrystaat
  7. International University Bremen
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1530557
Report Number(s):
PNNL-SA-140803
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 116; Journal Issue: 17
Country of Publication:
United States
Language:
English

Citation Formats

Mayer, Martin, Van Lessen, Valentin, Rohdenburg, Markus, Hou, Gao-Lei, Yang, Zheng, Exner, Rudiger M., Apra, 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, Rudiger M., Apra, 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, Rudiger M., Apra, Edoardo, Azov, Vladimir A., Grabowsky, SImon, Xantheas, Sotiris S., Asmis, Knut R., Wang, Xue-Bin, Jenne, Carsten, and Warneke, Jonas. Tue . "Rational design of an argon-binding superelectrophilic anion". United States. doi:10.1073/pnas.1820812116.
@article{osti_1530557,
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, Rudiger M. and Apra, 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 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 comprise a strong electrophilic center firmly embedded in a negativelycharged framework of exceptional stability. To validate our concept, we synthesized the percyano-dodecoborate [B12(CN)12]2-, the electronically most stable dianion ever investigated experimentally. It serves as a precursor for the generation of the monoanion [B12(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 first detection and characterization of this highly reactive, structurally stable anionic superelectrophile starts a new 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}
}