A new copper(I) thiocyanato thiocyanogen complex

Tobia, S. K.; Souaya, Eglal R.; Hanna, W.G.

doi:10.1016/s0277-5387(00)87003-5

Cited by 2 publications

(4 citation statements)

References 7 publications

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“…When solutions of CuCl 2 and NCS − in DMF or DMSO are mixed together, they form a characteristic blood red solution, which is the typical color of Cu(II)-thiocyanate complex ion species is reasonable. 44 Two peaks detected from IR transmission spectra of these model solutions were observed at ∼2055 and ∼2090 cm −1 (Figure 7). The peak observed at 2055-2056 cm −1 , which increases in intensity with increasing mole ratio, is due to the free NCS − ion.…”

Section: Cu/ncsmentioning

confidence: 95%

“…The shift is caused by redox chemistry 44 occurring in the model solution which produces a Cu(I) thiocyanate species from reduction of the Cu(II) ion by NCS − ion. The redox process is encouraged by addition of more NCS − ion relative to the CuCl 2 salt.…”

Section: Cu/ncsmentioning

confidence: 99%

“…In Figure 7, it is seen that as the mole ratio (CuCl 2 :NaSCN) was increased from 1:1 to 1:4, the peak maximum of the v(CN) stretch attributed to the Cu n+ -thiocyanate complex ion species decreased from 2093 to 2091 cm −1 in DMSO and from 2090 to 2084 cm −1 in DMF. The shift is caused by redox chemistry 44 occurring in the model solution which produces a Cu(I) thiocyanate species from reduction of the Cu(II) ion by NCS − ion. The redox process is encouraged by addition of more NCS − ion relative to the CuCl 2 salt.…”

Section: H438mentioning

confidence: 99%

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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

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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Section: Cu/ncsmentioning

confidence: 95%

Section: Cu/ncsmentioning

confidence: 99%

Section: H438mentioning

confidence: 99%

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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

Alwis

Mucalo

Ingham

et al. 2015

J. Electrochem. Soc.

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“…5(b), the peak at 2127 cm À1 arose from the destabilisation of TeCN À caused by the presence of the polarising Cu 2+ ions (from the Cu(II) salt), which led to the release of a free CN À ion. This then reacted with Cu(II) ions in a fortuitous redox sidereaction 29 (known to occur between Cu(II) and pseudohalide ions) that led to Cu(I) species being present in the mixture, which then became complexed with CN À ions to form the [Cu(CN) 2 ] À species that gives rise to the peak at 2127 cm À1 .…”

Section: Ir Data From the Model Solutions Prepared By Mixing Ni(ii) A...mentioning

confidence: 99%

A fundamental in situ IR spectroelectrochemical study of the electrical polarization of nickel, copper and gold electrodes in the presence of the unstable tellurocyanate ion in DMSO and DMF solutions

2015

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Subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS) studies have been performed for the first time on the interaction of the tellurocyanate ion (TeCN À ) with electrically polarised nickel (Ni), copper (Cu) and gold (Au) electrodes in dimethyl sulfoxide (DMSO) and dimethyl formamide (DMF) containing tetrabutylammonium perchlorate (TBAP) as a supporting electrolyte. In general, it was conclusively shown that the TeCN À ion decomposes at certain applied potentials on electrically polarized electrochemical cells to form elemental tellurium and cyanide (CN À ) ion. The cause of the decomposition was reasoned to be due to the presence of electrodissolved metal ions from the electrode, which destabilise the TeCN À ion through their polarising power as cations. The severity of the destabilisation was found to increase in the order Au + > Cu + > Ni 2+ , which is in general agreement with the relative polarising power of these metal ions. SNIFTIRS and IR transmission data from model solutions demonstrated that the metal complex ion speciation observed during the polarization experiments therefore arose directly from the interaction of the studied metal electrode with CN À ions released by decomposition, rather than with the TeCN À ion itself. The potential at which the electrochemical decomposition of the TeCN À ion occurred and its rate of decomposition depended on the type of metal electrode used. In general, the instability of the TeCN À ion in electrochemically polarized systems reflects its fundamental chemistry of decomposing in the presence of polarizing cations and that it may be of use as a sensor for these species in an electrochemical setting.

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A new copper(I) thiocyanato thiocyanogen complex

Cited by 2 publications

References 7 publications

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

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

A fundamental in situ IR spectroelectrochemical study of the electrical polarization of nickel, copper and gold electrodes in the presence of the unstable tellurocyanate ion in DMSO and DMF solutions

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A new copper(I) thiocyanato thiocyanogen complex

Cited by 2 publications

References 7 publications

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

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

A fundamental in situ IR spectroelectrochemical study of the electrical polarization of nickel, copper and gold electrodes in the presence of the unstable tellurocyanate ion in DMSO and DMF solutions

Contact Info

Product

Resources

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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

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