Raman and IR spectra of tetrachloro phosphonium salts of some tetrachlorate (MCI₄⁻) anions

Abstract

Complete Raman and IR spectra were recorded for the tetrachloro phosphonium salts of tetrachloro-aluminate, gallate, indate and ferrate. The spectra are interpreted on the basis of these complexes being of ionic structure of the general formula: PCL;MCI;. All the accordingly expected fundamentals have been observed and assigned.

Mechanism of Ferric Chloride Facilitating Efficient Lithium Extraction from Magnesium-Rich Brine with Tri-n-butyl Phosphate

“…To confirm that all metal chlorides were extracted as anionic chlorometallate complexes, the Aliquat 336 phase (without diluent) loaded from each metal chloride alone [except for AlCl 3 because of the low extraction of Al­(III)] was characterized by either Raman or UV–vis absorption spectra (Figure ). The Raman spectrum of the Fe­(III)–A336 phase shows three bands at 333, 134, and 109 cm –1 , respectively, which match very well with the Raman bands of [FeCl 4 ] − at 334, 132, and 112 cm –1 . , The bands at 321, 113, and 94 cm –1 in the Raman spectrum of the In­(III)–A336 phase are characteristic for [InCl 4 ] − , as reported at 321, 112, 89 cm –1. , The band at 291 cm –1 is attributed to [InCl 5 ] 2– , as reported at 293 cm –1 .…”

“…The Raman spectrum of the Li­(I)–Mg­(II)–Fe­(III)–TBP phase was recorded (Figure a). No extra bands are observable besides the three bands at 333, 132, and 109 cm –1 , which are the same as those for the Fe­(III)–A336 phase (Figure a) and correspond to [FeCl 4 ] − . , UV–vis absorption spectra of the Fe­(III)–A336 phase shows three peaks at around 531, 619, and 686 nm (Figure b), which are characteristic peaks of [FeCl 4 ] − . , The UV–vis absorption spectrum of the Li­(I)–Mg­(II)–Fe­(III)–TBP phase also shows the same maxima as that of the Fe­(III)–A336 phase with very close molar absorptivities at 531, 619, and 686 nm, respectively (Figure b). It is known that A336 extracts Fe­(III) as [FeCl 4 ] − . , The excellent match of the Raman and UV–vis absorption spectra of the Li­(I)–Mg­(II)–Fe­(III)–TBP phase with that of the Fe­(III)–A336 phase indicates that [FeCl 4 ] − is also the only species in the Li­(I)–Mg­(II)–Fe­(III)–TBP phase.…”

“…The Raman spectrum of the Fe(III)−A336 phase shows three bands at 333, 134, and 109 cm −1 , respectively, which match very well with the Raman bands of [FeCl 4 ] − at 334, 132, and 112 cm −1 . 41,42 The bands at 321, 113, and 94 cm −1 in the Raman spectrum of the In(III)−A336 phase are characteristic for [InCl 4 ] − , as reported at 321, 112, 89 cm −1. 43,44 The band at 291 cm −1 is attributed to [InCl 5 ] 2− , as reported at 293 cm −1 .…”

Tetrachloro- and Tetrabromoarsonium(V) Cations: Raman and 75As, 19F NMR Spectroscopic Characterization and X-ray Crystal Structures of [AsCl4][As(OTeF5)6] and [AsBr4][AsF(OTeF5)5]

“…48 When either solution or solid samples of [AsBr 4 ][AsF(OTeF 5 ) 5 ] are warmed, bromine is liberated (intense Raman band at 297 and 303 cm -1 at -113 °C). The room-temperature decomposition of [AsBr 4 ]-[AsF(OTeF 5 ) 5 ] in SO 2 ClF solvent has been monitored by 19 F NMR spectroscopy and occurs considerably more rapidly than that of [AsBr 4 ][As(OTeF 5 ) 6 ], with the AsF(OTeF 5 ) 5salt decomposing within 1 min and the As(OTeF 5 ) 6salt requiring several hours to decompose at room temperature. The roomtemperature decomposition of [AsBr 4 ][As(OTeF 5 ) 6 ] was also monitored by 75 As NMR spectroscopy (see 75 As NMR section), and because all arsenic containing decomposition products have local symmetries at 75 As that result in rapid quadrupolar relaxation of the allowed 75 As nuclear spin transitions, their 75 As resonances are too broad to be observed.…”

“…With the exception of bismuth, examples of tetrahalopnicogen(V) cations are known for all remaining group 15 elements. While only the fluoro-1,2 and chlorocations 3 are known for nitrogen, all the tetraphosphonium(V) cations have been synthesized and are the most fully characterized series of tetrahalopnicogen cations, with crystal structure determinations for PCl 4 + , 4-8 PBr 4 + , 9,10 and PI 4 + , 11 31 P NMR spectroscopic studies for PCl 4 + and PBr 4 + , [12][13][14][15][16] and vibrational studies for PCl 4 + , 5,8, [16][17][18][19] PBr 4 + , 16,18,[20][21][22] and PI 4 + . 23 The PF 4 + cation has only been characterized in the solid state by Raman spectroscopy.…”