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

Abstract

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.

Improvements of and Insights into the Isolation of Bismuth Polycations from Benzene Solution – Single‐Crystal Structure Determinations of Bi8[GaCl4]2 and Bi5[GaCl4]3

“…This is not very controversial, merely reinforcing the proposition that the GaCl 3 -benzene system can be regarded as a "pseudo-melt". [21] Of the two cations, Bi 5 3+ is obviously the most stable in solution; no traceable amounts of Bi 8 2+ were discovered using UV/Vis spectroscopy in earlier studies on this system. Likewise, only Bi 5 [GaCl 4 ] 3 is formed when precipitating using an alkane.…”

Highly Efficient and Selective CH Activation in Gallium‐Containing Molten‐Salt Systems

“…Depending on the amount of Ga 0 added to the reaction, the 71 Ga NMR spectrum shows signals in the typical ranges for Ga I and Ga III species (for low initial Ga 0 / chloromethane ratios) or only signals in the typical range for Ga I species (for high initial Ga 0 /chloromethane ratios). However, 71 Ga NMR spectra of Ga I are known to be much sharper than those of Ga III , [18][19][20] so that some Ga III might also have been formed in the latter case. Moreover, the acidity of the melt had a pronounced influence on the detection of the different Ga species, with Ga III appearing much more pronounced in neutral melts.…”

Synthesis of Main Group Polycations in Molten and Pseudo‐Molten GaBr3 Media

“…[3][4][5][6] This method is based on the extraordinarily high solubility of GaCl 3 in benzene, which renders a pseudo-melt behavior to the saturated solution. [7] Thus, it has been possible to repeat, at room temperature, several of the reactions previously performed in molten AlCl 3 . The major advantage of performing reactions at low temperatures is that it allows easier study of reactants and products in solution, using for instance spectroscopy.…”