Vibrational spectroscopy of metal methanesulfonates: M = Na, Cs, Cu, Ag, Cd

Abstract

In this work, we have used a combination of vibrational spectroscopy (infrared, Raman and inelastic neutron scattering) and periodic density functional theory to investigate six metal methanesulfonate compounds that exhibit four different modes of complexation of the methanesulfonate ion: ionic, monodentate, bidentate and pentadentate. We found that the transition energies of the modes associated with the methyl group (C–H stretches and deformations, methyl rock and torsion) are essentially independent of the mode of coordination. The SO3 modes in the Raman spectra also show little variation. In the infrared spectra, there is a clear distinction between ionic (i.e. not coordinated) and coordinated forms of the methanesulfonate ion. This is manifested as a splitting of the asymmetric S–O stretch modes of the SO3 moiety. Unfortunately, no further differentiation between the various modes of coordination: unidentate, bidentate etc … is possible with the compounds examined. While it is likely that such a distinction could be made, this will require a much larger dataset of compounds for which both structural and spectroscopic data are available than that available here.

Structure and vibrational spectroscopy of lithium and potassium methanesulfonates

“…The spectra of the two salts are broadly similar and do not hint at the complexity of the structure of the K salt. As seen in our previous work [12], the INS spectra are dominated by the methyl modes, particularly the rock (approx. 950 cm −1 ) and the torsion (200-300 cm −1 ).…”

“…As seen previously [12], only the methyl-related modes (C-H bends, rock and torsion), have significant intensity in the INS spectrum and demonstrates that the coupling between the CH 3 and SO 3 functionalities in the ion is weak. The strongest modes in the infrared and Raman spectra are motions of the sulfonate group, as these involve significant charge distortions that generate the intensity.…”

“…We have previously investigated the vibrational spectroscopy of the parent acid, methanesulfonic acid [ 11 ] and some of its salts, M = Na, Cs, Cu, Ag, Cd [ 12 ]. In the course of our previous work, we have observed a correlation between the type of bonding (ionic or complexed) present and the asymmetric S–O stretch mode in the infrared spectrum.…”

The di(thiourea)gold(I) complex [Au{S=C(NH2)2}2][SO3Me] as a precursor for the convenient preparation of gold nanoparticles

“…IR spectroscopy was used to investigate the nature of the ligand-to-metal coordination of 1. Therein, the presence of a non-coordinated mesylate anion was evidenced by the appearance of two bands at 1193 cm −1 (ν as (SO 3 )) and 1058 cm −1 (ν as (SO 3 )) [88]. The ν(NH) absorptions of the thiourea ligands at 3100-3400 cm −1 and the δ(NH 2 ) vibrations at 1600 cm −1 are representative for this family of complexes [89].…”

Indium electrodeposition from indium(iii) methanesulfonate in DMSO

“…However, a large number of metal methanesulfonates have already been characterized. [21][22][23] Furthermore, tin(II) methanesulfonate has been synthesized and used as precursor for tin electroplating from a bath composed of MSA and the ionic liquid 1-butyl-1-methyl-pyrrolidinium trifluoromethanesulfonate ([BMP][OTf]). 24 The prepared indium(III) methane-sulfonate was dissolved in DMSO.…”