Vibrational study of ionic association in aprotic solvents. 8. Copper(I) thiocyanate in soft donor solvents

Rannou, Jean; Chabanel, Martial

doi:10.1021/ic00208a040

Cited by 15 publications

(13 citation statements)

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“…In such cases, ionmolecule interactions are easily manifest in shifting the resonance frequencies of fundamental vibrational modes of a given molecule in vibrational spectra. Accordingly, such ion-molecule interactions have been extensively studied by FTIR experiments and theoretical methods for a few decades [1][2][3][4][5][6][7]. However, the effect of ions on vibrational dynamics of a given molecule has begun to be investigated recently with an advent of time-resolved vibrational spectroscopic techniques such as ultrafast infrared-Raman, infrared pump-probe (IR PP), and two-dimensional IR (2DIR) experiments [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22].…”

Section: Introductionmentioning

confidence: 99%

Effect of ion–molecule interaction on fermi-resonance in acetonitrile studied by ultrafast vibrational spectroscopy

2014

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Section: Introductionmentioning

confidence: 99%

Effect of ion–molecule interaction on fermi-resonance in acetonitrile studied by ultrafast vibrational spectroscopy

2014

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“…This assignment is supported by work reported by Kilmartin et al 8 who studied the formation mechanism of electrochemically deposited copper thiocyanate films on a copper anode, in which he assigned a Raman peak observed at 2175 cm −1 to an underlying CuSCN barrier film. Other workers reporting spectroscopic data for CuSCN 10,40,42 have also reported peaks at 2173 cm −1 . These studies have suggested what the nature of the solid CuSCN film on the Cu electrode in the present study could be.…”

Section: H442mentioning

confidence: 85%

“…13 The peak at 2087 cm −1 has been observed in earlier non-electrochemical studies by other workers and has been subject to various interpretations. 10,39,40 Forster and Goodgame reported IR data (run as nujol mulls) of a (C 2 H 5 ) 4 N[Cu(NCS) 4 ] salt which showed a strong ν(CN) stretching frequency at 2074 cm −1 . The solid was described as being either green or purple depending on the counter cation used to precipitate the solid 39 but dissolved in nitromethane or acetone to produce characteristic blood red solutions, for which no IR data were reported.…”

Section: Ir Spectra Of Cu/tbap/ncsmentioning

confidence: 99%

A Combined SNIFTIRS and XANES Study of Electrically Polarized Copper Electrodes in DMSO and DMF Solutions of Cyanate (NCO⁻), Thiocyanate (NCS⁻) and Selenocyanate (NCSe⁻) Ions

Alwis

Mucalo

Ingham

et al. 2015

J. Electrochem. Soc.

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A SNIFTIRS (subtractively normalized interfacial Fourier transform infrared spectroscopy) and X-ray absorption spectroscopy (XAS) study of electrically polarized copper electrodes in six polar aprotic solvent-based systems is presented. In the systems investigated, i.e. dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) solutions containing pseudohalide species of cyanate (NCO − ), thiocyanate (NCS − ) and selenocyanate (NCSe − ) codissolved with tetrabutylammonium perchlorate (TBAP), Cu was found to dissolve over a wide range of potentials to produce the corresponding Cu(I) pseudohalide and/or Cu(II) pseudohalide complex ion species. Insoluble deposited films were also observed at higher anodic applied potentials, thought to be CuSCN in the Cu/NCS − /DMSO or DMF systems, and solid K(SeCN) 3 in the Cu/NCSe − /DMSO or DMF systems respectively. The presence of the Cu(II) and/or Cu(I) oxidation states in complexes formed by polarization in Cu/pseudohalide ion systems in DMSO was clearly proven using XAS of cell solutions sampled after SNIFTIRS/electrical polarization experiments. In addition, Fourier transform infrared (FTIR) and X-ray absorption near edge spectroscopy (XANES) data obtained from model solutions prepared from mixing Cu(I) and/or Cu(II) salts with the respective pseudohalide ions in DMF and DMSO confirmed the speciation observed in the electrochemical experiments. A wide variety of organic solvents are used in technological processes, 1 for example, electrodepositing of copper from nonaqueous solutions.2 In battery applications, the use of organic solvents like acetonitrile, for instance, allows use of the battery at low ambient temperatures.3 However, extensive electrochemical characterization of metal electrode action (e.g. dissolution and electrodeposition) in non-aqueous (organic) media has been lacking. For instance, even though copper in DMF is widely used in industry, few electrochemical studies of copper dissolution/reduction in DMF have been reported. [4][5][6][7] The same may be said for electrodissolution studies in DMSO. Thiocyanate ion has often been used in copper electrochemistry, as it can mimic the behavior of halide ions like chloride, 8 which disrupt the passivation layer of oxide coatings formed on copper, and consequently increase the corrosion rate. The electrochemistry of metal electrode/pseudohalide systems has previously been studied by Bowmaker et al.9,10 and Kilmartin et al., 8,11 who looked at thiocyanate interaction with copper anodes and platinum electrodes. In addition, Bron and Holze have also reported in situ IR work for thiocyanate and cyanate interactions with gold and copper electrodes in aqueous electrolytes.12 In situ IR spectroelectrochemistry can provide detailed information on electrochemical processes. [13][14][15][16][17][18][19][20][21][22] It is also valuable for characterizing the molecular species generated, especially in conjunction with conventional electrochemical techniques such as cyclic voltammetry, which is unable to identify discrete molecula...

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“…To analyse the concentration of unpaired thiocyanate anion in DMTF solutions, it is necessary to obtain its IR molar absorption coefficient which, although known in several solvents, 15,16,29 has not yet been evaluated in DMTF solutions. Because of the low solubility of K(SCN) in DMTF (pK sp \ tetrabutylammonium thiocyanate has 3.3), 30 [NBu 4 (SCN)] been used as the non-associating solute.…”

Section: Integrated Molar Ir Absorption Coefficient Of the Thiocyanat...mentioning

confidence: 99%

“…To the best of our knowledge, the only vibrational spectroscopic (IR) studies published on silver(I) or copper(I) thiocyanate solutions in DMTF are from Chabanel and coworkers. 15,16 In these studies the thiocyanate structure of the ionic pair Ag(SCN), and the isothiocyanate structure of the corresponding Cu(NCS) are demonstrated. The equilibrium constant of the ionic pairing processes, however, are not reported in these works.…”

mentioning

confidence: 99%

Vibrational spectroscopic study of the ionic association and ion-pair structures in solutions of silver(I), copper(I) and thallium(I) thiocyanates in N,N-dimethylthioformamide

Alía¹,

Edwards²,

García-Navarro³

1998

Faraday Trans.

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Vibrational study of ionic association in aprotic solvents. 8. Copper(I) thiocyanate in soft donor solvents

Cited by 15 publications

References 0 publications

Effect of ion–molecule interaction on fermi-resonance in acetonitrile studied by ultrafast vibrational spectroscopy

Effect of ion–molecule interaction on fermi-resonance in acetonitrile studied by ultrafast vibrational spectroscopy

A Combined SNIFTIRS and XANES Study of Electrically Polarized Copper Electrodes in DMSO and DMF Solutions of Cyanate (NCO⁻), Thiocyanate (NCS⁻) and Selenocyanate (NCSe⁻) Ions

Vibrational spectroscopic study of the ionic association and ion-pair structures in solutions of silver(I), copper(I) and thallium(I) thiocyanates in N,N-dimethylthioformamide

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Vibrational study of ionic association in aprotic solvents. 8. Copper(I) thiocyanate in soft donor solvents

Cited by 15 publications

References 0 publications

Effect of ion–molecule interaction on fermi-resonance in acetonitrile studied by ultrafast vibrational spectroscopy

Effect of ion–molecule interaction on fermi-resonance in acetonitrile studied by ultrafast vibrational spectroscopy

A Combined SNIFTIRS and XANES Study of Electrically Polarized Copper Electrodes in DMSO and DMF Solutions of Cyanate (NCO−), Thiocyanate (NCS−) and Selenocyanate (NCSe−) Ions

Vibrational spectroscopic study of the ionic association and ion-pair structures in solutions of silver(I), copper(I) and thallium(I) thiocyanates in N,N-dimethylthioformamide

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A Combined SNIFTIRS and XANES Study of Electrically Polarized Copper Electrodes in DMSO and DMF Solutions of Cyanate (NCO⁻), Thiocyanate (NCS⁻) and Selenocyanate (NCSe⁻) Ions