On the thermal properties of some di- and tri-alkylammonium tetrafluoroborates

Zabinska, G.; Ferloni, P.; Sanesi, M.

doi:10.1016/0040-6031(88)87463-x

Cited by 8 publications

(8 citation statements)

References 6 publications

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“…The structures of alkylammonium and alkylphosphonium salts change along with their phase transitions upon heating, which was investigated by various techniques like differential scanning calorimetry (DSC), X-ray diffraction (XRD), and nuclear magnetic resonance (NMR). 13,15,17,18,[21][22][23][24][25][26][27][28][29] Our recent study of the tetraalkylammonium salts of BF 4 À and PF 6 À revealed that the structural type of their plastic crystal phases depends on the size of the cation, which follows the radius ratio rule. 30 , and PF 6 À ).…”

Section: Introductionmentioning

confidence: 99%

Formation of a solid solution between [N(C₂H₅)₄][BF₄] and [N(C₂H₅)₄][PF₆] in crystal and plastic crystal phases

Matsumoto

Nonaka

Wang

et al. 2017

Phys. Chem. Chem. Phys.

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The phase behavior of [N][BF] and [N][PF] (N = tetraethylammonium cation) binary systems has been investigated in the present study. Differential scanning calorimetry revealed that the crystal-to-plastic-crystal transition temperature decreases upon mixing the two salts, with a minimum at x([N][PF]) = 0.4, where x([N][PF]) denotes the molar fraction of [N][PF]. Powder X-ray diffraction analysis indicated the formation of a solid solution with a rock-salt type structure in the plastic crystal phase at all ratios and the lattice parameter a changes according to Vegard's law. In the crystal phase, two solid solution phases based on the structures of the single salts are observed. Raman spectroscopy confirmed the changes in the solid-solid transition temperature as observed by differential scanning calorimetry. Consequently, in the resulting phase diagram, the solid solution is formed in a wide x([N][PF]) range for both the crystal and plastic crystal phases.

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Section: Introductionmentioning

confidence: 99%

Formation of a solid solution between [N(C₂H₅)₄][BF₄] and [N(C₂H₅)₄][PF₆] in crystal and plastic crystal phases

Matsumoto

Nonaka

Wang

et al. 2017

Phys. Chem. Chem. Phys.

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“…The crystallographic studies were carried out at room temperature and the assignment of these species as an iminium derivative is supported by the bond distances and angles at C4. The C=N distances of 12, 13 and 14 are 1.313(6), 1.306(12) and 1.308(10) Å, respectively, which is appropiate for a double bond, whereas bonds between nitrogen and the carbon atoms of the corresponding cyclic amines are longer N-C7 1.491 (6), N-C11 1.494(7) 12; N-C7 1.464(12), N-C10 1.441(16) 13; and N-C7 1.479(11), N-C10 1.477(10) 14 Å. The molecular structures are presented in Figures 1-3, respectively.…”

Section: Methodsmentioning

confidence: 99%

“…Dicationic ruthenium compounds [(arene)Ru(thiophene)] 2+ containing thiophene, 2-methylthiophene, 2,5-dimethylthiophene and 1,2,3,4-tetramethylthiophenes react with ammonia to give salts of the formula [(arene)Ru(SC 4 R 4 NH 2 )]X (arene = C 6 Me 6 or cymene; R = H, Me; X = BF 4 , PF 6 or OTf). The coordinated thiophene, as well as the substituted 2-and 2,5-methyl derivatives undergo C-S cleavage in order to give the corresponding iminium thiolate derivatives.…”

Section: Introductionmentioning

confidence: 99%

Aminolysis of iridium thiophene compounds

Paz-Sandoval¹,

Cervantes-Vásquez²,

Paz‐Michel³

2007

Arkivoc

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“…Alkylammonium and alkylphosphonium salts have been the topics of structural studies because they exhibit a variety of structural changes during thermal transitions. [1][2][3][4][5][6][7][8][9][10] Their highest temperature solid phase is particularly interesting and is characterized by disordering of the globular or pseudo-globular component ions. These phases are often referred to as ionic plastic crystals (IPCs) and have been attracting attention recently because they can be used as solid-state electrolytes in the construction of safe and reliable electrochemical devices.…”

Section: Introductionmentioning

confidence: 99%

“…-ray diffraction pattern of [P 3 ][PF 6 ] is indexed as a hexagonal lattice with a = 9.702(4) Å, c = 12.9888(11) Å, and V = 1050.7(11) Å3 . The Z value is estimated to be 2 through comparison with the FUV of the low-temperature phase of [N 3 ][BF 4 ] (397 Å 3 ) 39.…”

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The structural classification of the highly disordered crystal phases of [N_n][BF₄], [N_n][PF₆], [P_n][BF₄], and [P_n][PF₆] salts (N_n⁺= tetraalkylammonium and P_n⁺= tetraalkylphosphonium)

Matsumoto

Harinaga

Tanaka

et al. 2014

Phys. Chem. Chem. Phys.

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The structures of 16 symmetric tetraalkylammonium (Nn(+)) and tetraalkylphosphonium (Pn(+)) salts ([Nn][BF4], [Nn][PF6], [Pn][BF4], and [Pn][PF6], where n = 1 to 4, and denotes the number of carbon atoms in each alkyl chain) have been investigated by X-ray diffraction in order to elucidate the effect of ion size on the disordered structure of organic salts. All the salts exhibit one or more solid-solid phase transitions in differential scanning calorimetric curves. Powder X-ray diffraction revealed that the highest temperature solid phase of these salts belongs to a crystal system with a high cubic or hexagonal symmetry. The structures are classified into 5 different types: CsCl', NaCl, NaCl', inverse NiAs, and TBPPF6. The CsCl'-type whose octant corresponds to the original CsCl unit cell is observed for [N1][PF6] owing to the orientational difference for the cation or the anion. The NaCl-type structure is observed for the N2(+) and P2(+) salts while the NaCl'-type structure is observed for [N3][PF6], where the configuration of ions is based on the NaCl-type but the four equivalent positions in the original NaCl lattice split into two sets of equivalent positions (three and one). The inverse NiAs structure is observed for [P3][PF6]. Single-crystal X-ray diffraction reveals that the disordering of ions in [P4][PF6] becomes more significant with increasing temperature. The new structure of a cubic phase, the TBPPF6-type structure, is found for the salts with long alkyl chains. The structure is roughly determined at 333 K and the ions therein are highly disordered but not rotating. The validity of the radius ratio rule is confirmed through appropriate assessment of the ion size.

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On the thermal properties of some di- and tri-alkylammonium tetrafluoroborates

Cited by 8 publications

References 6 publications

Formation of a solid solution between [N(C₂H₅)₄][BF₄] and [N(C₂H₅)₄][PF₆] in crystal and plastic crystal phases

Formation of a solid solution between [N(C₂H₅)₄][BF₄] and [N(C₂H₅)₄][PF₆] in crystal and plastic crystal phases

Aminolysis of iridium thiophene compounds

The structural classification of the highly disordered crystal phases of [N_n][BF₄], [N_n][PF₆], [P_n][BF₄], and [P_n][PF₆] salts (N_n⁺= tetraalkylammonium and P_n⁺= tetraalkylphosphonium)

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On the thermal properties of some di- and tri-alkylammonium tetrafluoroborates

Cited by 8 publications

References 6 publications

Formation of a solid solution between [N(C2H5)4][BF4] and [N(C2H5)4][PF6] in crystal and plastic crystal phases

Formation of a solid solution between [N(C2H5)4][BF4] and [N(C2H5)4][PF6] in crystal and plastic crystal phases

Aminolysis of iridium thiophene compounds

The structural classification of the highly disordered crystal phases of [Nn][BF4], [Nn][PF6], [Pn][BF4], and [Pn][PF6] salts (Nn+= tetraalkylammonium and Pn+= tetraalkylphosphonium)

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Formation of a solid solution between [N(C₂H₅)₄][BF₄] and [N(C₂H₅)₄][PF₆] in crystal and plastic crystal phases

Formation of a solid solution between [N(C₂H₅)₄][BF₄] and [N(C₂H₅)₄][PF₆] in crystal and plastic crystal phases

The structural classification of the highly disordered crystal phases of [N_n][BF₄], [N_n][PF₆], [P_n][BF₄], and [P_n][PF₆] salts (N_n⁺= tetraalkylammonium and P_n⁺= tetraalkylphosphonium)