Rational design of an argon-binding superelectrophilic anion

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

doi:10.1073/pnas.1820812116

Title: Rational design of an argon-binding superelectrophilic anion

Journal Article · Tue Apr 23 00:00:00 EDT 2019 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1820812116· OSTI ID:1530557

Mayer, Martin ^[1]; Van Lessen, Valentin ^[2]; Rohdenburg, Markus ^[3];

^[4]; Yang, Zheng ^[5]; Exner, Rudiger M. ^[2];

^[5]; Azov, Vladimir A. ^[6]; Grabowsky, SImon ^[7];

^[5]; Asmis, Knut R. ^[1];

^[5]; Jenne, Carsten ^[2]; Warneke, Jonas ^[4]

Universitat Leipzig
Bergische Universitat Wuppertal
Universitat Bremen
UNIVERSITY PROGRAMS
BATTELLE (PACIFIC NW LAB)
Universiteit van die Vrystaat
International University Bremen

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.

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Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1530557

Report Number(s):: PNNL-SA-140803

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Vol. 116, Issue 17

Country of Publication:: United States

Language:: English

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Quantum chemical prediction of a superelectrophilic dianion and its binding with noble gas atoms Joshi, Meenakshi; Ghanty, Tapan K. Chemical Communications, Vol. 55, Issue 95 https://doi.org/10.1039/c9cc08049j	journal	January 2019
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