An infrared study of gallium chlorides and bromides in benzene and n-heptane

Kinsella, E.; Chadwick, James; Coward, J.

doi:10.1039/j19680000969

Cited by 23 publications

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“…Such solutions are composed of two liquid phases with the greater part of the chloride in the lower, denser phase. 16 No changes in the solvent bands upon dissolution of Ga2Cl, were observed in any of the phases, nor were any bands found at 2500 cm-' apart from those which belong to the solvent. The same spectral invariance of the solvent is also observed in the 13C NMR spectra (Table 2), in which no effect on the benzene signal can be detected upon dissolution of Ga2Cl,.…”

Section: Solidmentioning

confidence: 86%

The structure of solutions of gallium(I) chloride in benzene

Ulvenlund¹,

Wheatley²,

Bengtsson³

1995

J. Chem. Soc., Dalton Trans.

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The structure of benzene solutions of Ga[GaCI,] and Ga[Ga,CI,] has been investigated by 13C and ,lGa NMR, Raman spectroscopy and liquid X-ray scattering (LXS). Assignments of the vibrational spectra are based on a reinvestigation of the liquid Ga-GaCI, system. The results for the Ga[GaCI,]-C,H, system are in agreement with the view that an ion pair between Ga+ and GaCI,-, which lowers the symmetry of the GaCI,-ion from Td to C, , or lower, is formed. Spectroscopic effects indicating a complex formation between Ga+ and benzene are weak. The salt Ga[Ga,CI,] was found to be extremely soluble in benzene ( > 50% w/w). The results imply that in such solutions the Ga-CI,-Ga bridge in the Ga,CI,-ion is bent and the ion pairing between Ga' and Ga,CI,-takes place via the bridging chloride ion of the latter ion. Results from LXS show that the Ga"'-CI,, distance is remarkably long, 2.85 A (24% longer than in solid K[Ga,CI,]). For this system, ,lGa and 13C NMR as well as Raman spectroscopic results clearly indicate complex formation between Gal and benzene.

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Section: Solidmentioning

confidence: 86%

The structure of solutions of gallium(I) chloride in benzene

Ulvenlund¹,

Wheatley²,

Bengtsson³

1995

J. Chem. Soc., Dalton Trans.

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“…Calibration of the instrument from m/z 91 to 1133 was accomplished with a CsI/glycerol mixture. In most cases, [10][11][12][13][14][15] scans were acquired per sample. After the desired number of scans were obtained, the sample was removed and the probe tip dipped in dilute nitric acid, rinsed with distilled water and then acetone, and dried before the next experiment.…”

Section: Methodsmentioning

confidence: 99%

Fast atom bombardment mass spectrometry of low temperature chloroaluminate and chlorogallate melts

Wicelinski¹,

Gale²,

Pamidimukkala³

et al. 1988

Anal. Chem.

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Fast atom bombardment (FAB) mass spectrometric analyses of r m temperature cMoroalunlnate and cMorogallate mdten salts are described. Melts composed of AICI, or GaCi, with 1-butyipyridinium chloride (BPC) or l-methyi-3-ethyiimidazdlum chloride (MEIC) were investigated to determine the nature of the Ai or Ga species as a function of Lewis acidity. Acidic melts contain a molar excess of AICI, or GaCi,, whereas basic systems have a molar excess of the organlc chloride. Mass spectra of negative ions were selected by wing a Kratos MSBORFA, double focusing, forward geometry mass spectrometer. Ankns such as AIC14-, Ai2Ci,-, AiSCi8-, QaC14-, and Ga2Ci,-were detected along with subvalent monomer, dimer, and mlxed-valent species. I n addC tion, various oxychloro and hydroxychioro species of Ai and Ga have been klentifled as well as (catkrt-dlanlon) aggregate ions. Results obtained reflect the surface condensed phase chemistry and gas phase reaction pathways established by the energy imparted by the FAB ionization process.The technique of fast atom bombardment mass spectrometry (FAB-MS) was pioneered by Barber and co-workers ( I ) .They developed an ion source that accommodated nonvolatile materials (high molecular weight compounds of biological and biomedical importance), utilized the phenomenon of ion sputtering, and employed a beam of fast neutral atoms. This bombardment by 5-10 keV energy particles does not require thermal sample volatilization and thus avoids direct thermal decomposition. In addition, the method works for either positive or negative ions while providing structurally significant fragmentation. Bojeson (2) demonstrated that the application of this technique to inorganic salts dissolved in glycerol (for example) was a natural extension. By his investigation of coordination compounds, Bojeson showed that FAB-MS was a useful analytical tool for the study of strongly bound metal-organic ligand complexes. Recently, Ackerman et al. (3) have reported FAB-MS analyses (positive ion mode) of A1C13/ 1-butylpyridinium chloride (BPC) melts. Although characteristic changes in the pceitive ion mass spectra reflected changes in melt composition (Lewis acidity), an overall assessment of the anions present was not possible for their instrument. Conversely, Franzen et al. (4) have used secondary ion mass spectrometry (SIMS) with a 5-keV cesium primary ion beam to identify the major anionic species (AlCl;, A12C17-, and C1-) in chloroaluminate melts. Since the room temperature 1-butylpyridinium chloride or 1-methyl-3-ethylimidazolium (MEIC) chloroaluminate and chlorogallate melts PreseTable I. FAB Spectra of Acidic Chloroaluminate Melts m/za 2:l AlC13/BPCb 1.5:l AlC13/MEICb 149 169 247 283 301 325 361 381 399 459 2.3 15.0 16.4 17.6 1.2 6.6 6.5 3.5 6.5 3.9 1.3 36.3 11.2 15.1 1.0 3.4 0.6 0.9 2.6"Highest ion intensity in cluster. bAbsolute percent total intensity, i.e., the sum of ion currents of an isotopic cluster as percent of total ion current.are not fully characterized from the standpoint of higher anionic species such as...

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“…The band of 366 cm-' is thus caused by a hydrolysis product, presumably GaCl,(OH)-. 22 Weak 'H NMR signals at 6 4.13 and 4.10 in the benzene and mesitylene systems, respectively, are found in the hydrolysed solutions. The shifts differ significantly from those obtained from the neat solvents saturated with water (6 4.31 and 4.77 in benzene and mesitylene, respectively).…”

Section: Resultsmentioning

confidence: 94%

“…This behaviour has previously been observed for benzene solutions by IR spectroscopy and thus the band is also IR active. 22 At the same time the Raman bands assigned to the gallium(n1)-benzene/rnesitylene interaction disappear, suggesting a breaking of the arene-gallium(m) bonds. The band of 366 cm-' is thus caused by a hydrolysis product, presumably GaCl,(OH)-.…”

Section: Resultsmentioning

confidence: 99%

“…A priori, bands not attributable to Ga2C1, may be assigned in four different ways: (1) from a hydrolysis product [e.g. GaCl,(OH)-1; a weak IR band at 363 cm-' in GaC1,-benzene solution has been explained in this way; 22 (2) from chlorogallate(m) ions; such ions have previously been found to exist in the 'red oils' of Friedel-Crafts systems MC1,-arene-HC1 (M = A135 or Ga)34 and are thus soluble in aromatics; (3) from monomeric GaCl, in equilibrium with Ga2Cl,; (4) from an isomer of Ga2Cl, (e.g. C1,Ga-Cl-GaCl,) which has been inferred by Raman spectroscopy of the AlBr,benzene system and discussed in the Introduction.…”

Section: Resultsmentioning

confidence: 99%

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Spectroscopic investigation of concentrated solutions of gallium(III) chloride in mesitylene and benzene

Ulvenlund¹,

Wheatley²,

Bengtsson³

1995

J. Chem. Soc., Dalton Trans.

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The metal-arene interaction in concentrated binary mixtures of GaCI, and mesitylene or benzene has been investigated using multinuclear ('H, Y, 71Ga) N M R , Raman and UV/VlS spectroscopy as well as liquid X-ray scattering. The effects of hydrolysis and radiolysis of such mixtures have also been studied using UV/VlS, EPR and IR spectroscopy. Gallium(iit) chloride has been found to be monomeric in mesitylene and to form q6 complexes with this arene. A structural determination of this complex in solution yielded a Ga-C distance of 2.20 A and a GaCI, moiety with C," symmetry and Ga-CI distances of 2.1 0 A. In benzene, GaCI, exists as a mixture of the CI,Ga(p-C1)2GaC12 dimer and one or several other species, containing terminal GaCI, groups of C,ysymmetry, e.g. the dimer isomer CI,Ga(p-CI)GaCI, and monomeric GaCI,. The complex with benzene is weaker than with mesitylene and the co-ordination mode cannot be unambiguously elucidated. Hydrolysis of the GaCI,-C,H, system produced a darkly coloured precipitate showed by IR spectroscopy to be a mixture of poly(p-phenylene) and other polymeric species, probably rneta-su bstituted, chlorinated and hydroxylated polyphenylenes. On the basis of 71Ga N M R results, it is suggested that the formation of this polymer proceeds via protonated Wheland intermediates, rather than direct oxidation of benzene by Gall'. Radiolysis of the mixtures of GaCI, with mesitylene and benzene yielded radicals, according to EPR spectroscopy. In benzene solution the formation of radicals is accompanied by reduction of Gall' to Gal. No formation of solid polymers could be detected.. 75,446.

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An infrared study of gallium chlorides and bromides in benzene and n-heptane

Cited by 23 publications

References 0 publications

The structure of solutions of gallium(I) chloride in benzene

The structure of solutions of gallium(I) chloride in benzene

Fast atom bombardment mass spectrometry of low temperature chloroaluminate and chlorogallate melts

Spectroscopic investigation of concentrated solutions of gallium(III) chloride in mesitylene and benzene

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