Ionic liquids containing the triply negatively charged tricyanomelaminate anion and a B(C₆F₅)₃ adduct anion

Voss, Karsten; Becker, Martin; Villinger, Alexander; Emel'yanenko, Vladimir N; Hellmann, Robert; Kirchner, Barbara; Uhlig, Frank; Verevkin, Sergey P; Schulz, Axel

doi:10.1002/chem.201101946

Ionic liquids containing the triply negatively charged tricyanomelaminate anion and a B(C₆F₅)₃ adduct anion

Publication date

2011-11-25

Document type

Research article

Author

Voss, Karsten

Becker, Martin

Villinger, Alexander

Emel'yanenko, Vladimir N

Hellmann, Robert

Kirchner, Barbara

Uhlig, Frank

Verevkin, Sergey P

Schulz, Axel

Organisational unit

Universität Rostock

DOI

10.1002/chem.201101946

URI

https://openhsu.ub.hsu-hh.de/handle/10.24405/14501

Scopus ID

2-s2.0-81755186844

Pubmed ID

22052735

Series or journal

Chemistry - a European journal

ISSN

0947-6539

1521-3765

Periodical volume

17

Periodical issue

48

First page

13526

Last page

13537

Peer-reviewed

✅

Part of the university bibliography

Nein

Language

English

Keyword

Density functional calculations

Ionic liquids

Melaminates

Nitrogen heterocycles

Thermochemistry

Abstract

Room-temperature ionic liquids containing the triply charged tricyanomelaminate (tcmel) ion [C(3)N(6)(CN)(3)](3-) were synthesized. The 1-methyl-3-methylimidazolium (MMIm), 1-ethyl-3-methylimidazolium (EMIm), and 1-butyl-3-methylimidazolium (BMIm) salts of the tricyanomelaminate ion have glass transition temperatures (-6, -20, and -30 °C) similar to those found for the analogous monomeric dicyanoamide salts. They are thermally stable up to over 200 °C and dissolve in polar organic solvents. Addition of B(C(6)F(5))(3) to M(3) [tcmel] (M=Na, MMIm, EMIm, BMIm) yields salts containing the very voluminous adduct ion [C(3)N(6) {CN·B(C(6)F(5))(3)}(3)](3-) (tcmel_3B). The solid-state structure of [MMIm](3-) [tcmel] shows only long cation···anion contacts but in large number, while the solid-state structure of [Na(THF)(3)](3-) [tcmel_3B]·1.76 THF displays strong interactions of the sodium cation with the amido nitrogen atoms of the anion. Hence this adduct anion cannot be regarded as a weakly coordinating anion. A similar situation is found for the MMIm salt, [MMIm](3) [tcmel_3B]·2.66 CH(2)Cl(2), in which weak hydrogen bonds with the acidic proton of the MMIm ion are observed. On the basis of computations the energetics, structural trends, and charge transfer of adduct anion formation were studied.

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