Synthetic Methods for Preparing Ionic Liquids Containing Hypophosphite and Carbon‐Extended Dicyanamide Anions

Maciejewski, John P.; Gao, Haixiang; Shreeve, Jean’ne M.

doi:10.1002/chem.201203740

Cited by 13 publications

(5 citation statements)

References 21 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…1-Butyl-3methylimidazolium vinylogous dicyanamide (BMIM + VDCA − ) was synthesized as described. 17 1-Ethyl-2,3-dimethylimidazolium dicyanamide (EMMIM + DCA − ) was synthesized according to the procedure in ref 1.…”

Section: Methodsmentioning

confidence: 99%

“…1-Ethyl-3-methylimidazolium dicyanamide (EMIM + DCA – ≥98.5% purity), 1-ethylimidazolium thiocyanate (EMIM + SCN – , ≥99% purity), and 1-butyl-3-methylimidazolium thiocyanate (BMIM + SCN – , ≥95% purity) were purchased from Fluka and used without further purification. 1-Butyl-3-methylimidazolium vinylogous dicyanamide (BMIM + VDCA – ) was synthesized as described . 1-Ethyl-2,3-dimethylimidazolium dicyanamide (EMMIM + DCA – ) was synthesized according to the procedure in ref .…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Thermal Decomposition Mechanisms of Alkylimidazolium Ionic Liquids with Cyano-Functionalized Anions

Chambreau

Schenk²,

Sheppard³

et al. 2014

J. Phys. Chem. A

View full text Add to dashboard Cite

Because of the unusually high heats of vaporization of room-temperature ionic liquids (RTILs), volatilization of RTILs through thermal decomposition and vaporization of the decomposition products can be significant. Upon heating of cyano-functionalized anionic RTILs in vacuum, their gaseous products were detected experimentally via tunable vacuum ultraviolet photoionization mass spectrometry performed at the Chemical Dynamics Beamline 9.0.2 at the Advanced Light Source. Experimental evidence for di- and trialkylimidazolium cations and cyano-functionalized anionic RTILs confirms thermal decomposition occurs primarily through two pathways: deprotonation of the cation by the anion and dealkylation of the imidazolium cation by the anion. Secondary reactions include possible cyclization of the cation and C2 substitution on the imidazolium, and their proposed reaction mechanisms are introduced here. Additional evidence supporting these mechanisms was obtained using thermal gravimetric analysis-mass spectrometry, gas chromatography-mass spectrometry, and temperature-jump infrared spectroscopy. In order to predict the overall thermal stability in these ionic liquids, the ability to accurately calculate both the basicity of the anions and their nucleophilicity in the ionic liquid is critical. Both gas phase and condensed phase (generic ionic liquid (GIL) model) density functional theory calculations support the decomposition mechanisms, and the GIL model could provide a highly accurate means to determine thermal stabilities for ionic liquids in general.

show abstract

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Thermal Decomposition Mechanisms of Alkylimidazolium Ionic Liquids with Cyano-Functionalized Anions

Chambreau

Schenk²,

Sheppard³

et al. 2014

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…For the synthesis of new hypergolic ILs, the design of novel anions with reducing properties is of critical importance (Table ). Recently, some hypophosphite (HP) and carbon-extended dicyanamide anions (i.e., N -(2,2-dicyanovinyl)cyanamide ( v DCA) and N , N ′-dicyanoformamidine (DCF) anions) were also used for the design and synthesis of new hypergolic ILs (Scheme ) . Here, the hypophosphite (HP) anion was chosen for the construction of hypergolic ILs mainly considering its inherent reducing properties, while the N -(2,2-dicyanovinyl)cyanamide ( v DCA) and N , N ′-dicyanoformamidine (DCF) anions were used mainly due to their structural analogy to the DCA anion.…”

Section: Applications Of Eils As Hypergolic Fuelsmentioning

confidence: 99%

Energetic Ionic Liquids as Explosives and Propellant Fuels: A New Journey of Ionic Liquid Chemistry

2014

View full text Add to dashboard Cite

“…Moreover, very recently some ionic liquids containing hypophosphite (HP) and carbon‐extended dicyanamide anions (i.e., N ‐(2,2‐dicyanovinyl)cyanamide (vDCA) and N , N ′‐dicyanoformamidine (DCF) anions) were also prepared, and their potential as hypergolic ionic fuels were preliminarily explored (Scheme ) 16. In this design strategy, the hypophosphite (HP) anion was chosen for the construction of hypergolic ionic liquids mainly due to its ability to act as a strong reducing reagent.…”

Section: Designing Hypergolic Ionic Fuels: Nitrocyanamide (Nca) Anionmentioning

confidence: 99%

Ionic Liquid Propellants: Future Fuels for Space Propulsion

Zhang¹,

Shreeve²

2013

Chemistry A European J

Self Cite

104

View full text Add to dashboard Cite

Use of green propellants is a trend for future space propulsion. Hypergolic ionic liquid propellants, which are environmentally-benign while exhibiting energetic performances comparable to hydrazine, have shown great potential to meet the requirements of developing nontoxic high-performance propellant formulations for space propulsion applications. This Concept article presents a review of recent advances in the field of ionic liquid propellants.

show abstract

Synthetic Methods for Preparing Ionic Liquids Containing Hypophosphite and Carbon‐Extended Dicyanamide Anions

Cited by 13 publications

References 21 publications

Thermal Decomposition Mechanisms of Alkylimidazolium Ionic Liquids with Cyano-Functionalized Anions

Thermal Decomposition Mechanisms of Alkylimidazolium Ionic Liquids with Cyano-Functionalized Anions

Energetic Ionic Liquids as Explosives and Propellant Fuels: A New Journey of Ionic Liquid Chemistry

Ionic Liquid Propellants: Future Fuels for Space Propulsion

Contact Info

Product

Resources

About