Synthesis and Structure of Ionic Liquids Containing the ­[Al(OC₆H₄CN)₄]^– Anion

Abstract

The synthesis, structure, and physical properties of ionic liquids (IL) bearing the novel [Al(O–C6H4–CN)4]– ion as counterion to the commonly used [NR4]+, [PR4]+ and imidazolium ions are reported. Both the influence of the alkyl chain length as well as the functionalization with cyano groups is studied. These ILs are easily obtained by reaction of Ag[Al(O–C6H4–CN)4] with the corresponding ammonium, phosphonium, and imidazolium halides. The stability towards electrophilic cations was investigated. All prepared salts have a window for the liquid phase of ca. 200 °C and are thermally stable up to 450 °C. The solid‐state structures reveal only weak cation···anion and anion···anion interactions in accord with the observed low melting points (glass transition points).

[B(O–C6H4–CN)4]– based Silver and Copper Coordination Polymers

“…Generally, the shift to lower wave numbers (ca. 2220 cm –1 ) indicates a decrease of interionic interaction by the CN group as shown for [Al(O–C 6 H 4 –CN) 4 ] – containing salts of organic cations 35. In turn, the coordination of a Lewis acid to a NC– R species causes a significant band shift to higher wave numbers {cf.…”

“…This kind of interaction was already discussed in [Al(O–C 6 H 4 –CN) 4 ] – ‐based ionic liquids, for which similar structural features were described [cf. C ··· O 3.367(2) Å] 35. The overall assembly, formed by these C–H ··· O‐contacts, is shown in Figure 7.…”

“…C···O 3.367(2) Å]. [35] The overall assembly, formed by these C-H···O-contacts, is shown in Figure 7. Two sheet-like framework of 5b are arranged in staggered fashion along the b axis.…”

“…2220 cm -1 ) indicates a decrease of interionic interaction by the CN group as shown for [Al(O-C 6 H 4 -CN) 4 ] -containing salts of organic cations. [35] In turn, the coordination of a Lewis acid to a NC-R species causes a significant band shift to higher wave numbers {cf. Na[(F 5 C 6 ) 3 B·O-C 6 H 4 -CN·B(C 6 F 5 ) 3 ]: IR 2309 cm -1 , Raman 2312 cm -1 }.…”

Lewis Acid Catalyzed Synthesis of Cyanidoborates

“…Recently, Finze et al [17] reported more efficient syntheses of M[BF(CN) 3 ] (M = Na, K) with Me 3 SiCl as a catalyst independently to our work on catalyzed F -/CNsubstitution reactions. [18][19][20][21][22][23][24] Cyanidoborate salts are used widely, [25][26][27][28][29] for example, as starting materials for light-element ceramics, [30] the generation of 3D coordination polymers, or as anions in ionic liquids (ILs). [8,11,13,[31][32][33] Cyanidoborate-based ILs can be obtained readily through salt metathesis reactions.…”