Spectroscopic and magnetic studies of some copper(II) and chromium(III) complexes with dithiophosphonates as ligands

Haiduc, Ionel; David, L.; Cozar, O.; Micu-Semeniuc, Rodica; Mezei, Gellert; Armenean, M.

doi:10.1016/s0022-2860(98)00931-4

Cited by 18 publications

(16 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…27,45,46 Moreover, the α 2 value of 0.5 is within the limits calculated by Hoffmann et al 29 for square-planar copper−sulfur complexes The low α 2 value of 1 red indicates a large delocalization of the unpaired electron density onto the sulfur atoms, as it was suggested for other {CuS 4 } complexes. 27,29,45,46 DFT Calculations. To understand the electronic structure of the synthesized complex 1 red , and support the strong covalency of its Cu−S bonds revealed by the EPR experiments, we have carried out DFT calculations.…”

Section: ■ Introductionsupporting

confidence: 85%

One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O₂/HO^–

et al. 2014

View full text Add to dashboard Cite

The complex [Ph4P]2[Cu(bdt)2] (1(red)) was synthesized by the reaction of [Ph4P]2[S2MoS2CuCl] with H2bdt (bdt = benzene-1,2-dithiolate) in basic medium. 1(red) is highly susceptible toward dioxygen, affording the one electron oxidized diamagnetic compound [Ph4P][Cu(bdt)2] (1(ox)). The interconversion between these two oxidation states can be switched by addition of O2 or base (Et4NOH = tetraethylammonium hydroxide), as demonstrated by cyclic voltammetry and UV-visible and EPR spectroscopies. Thiomolybdates, in free or complex forms with copper ions, play an important role in the stability of 1(red) during its synthesis, since in its absence, 1(ox) is isolated. Both 1(red) and 1(ox) were structurally characterized by X-ray crystallography. EPR experiments showed that 1(red) is a Cu(II)-sulfur complex and revealed strong covalency on the copper-sulfur bonds. DFT calculations confirmed the spin density delocalization over the four sulfur atoms (76%) and copper (24%) atom, suggesting that 1(red) has a "thiyl radical character". Time dependent DFT calculations identified such ligand to ligand charge transfer transitions. Accordingly, 1(red) is better described by the two isoelectronic structures [Cu(I)(bdt2, 4S(3-,)*)](2-) ↔ [Cu(II)(bdt2, 4S(4-))](2-). On thermodynamic grounds, oxidation of 1(red) (doublet state) leads to 1(ox) singlet state, [Cu(III)(bdt2, 4S(4-))](1-).

show abstract

Section: ■ Introductionsupporting

confidence: 85%

One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O₂/HO^–

et al. 2014

View full text Add to dashboard Cite

show abstract

“…Some representative data marked by points have parameters collected in Table 1 (with Refs. [11][12][13][14][15][16]). Remarkable larger slope of the correlation line for CuS 4 is not well understood.…”

Section: Introductionmentioning

confidence: 99%

EPR and ESE of CuS4 complex in Cu(dmit)2: g-Factor and hyperfine splitting correlation in tetrahedral Cu–sulfur complexes

Hoffmann

Goslar

Lijewski

et al. 2013

Journal of Magnetic Resonance

View full text Add to dashboard Cite

“…For example gold-thiophosphonate complexes are used in a variety of applications in modern technology [6] such as photosensitizers for photographic emulsions [7], and luminescence-based chemical sensors [8]. The coordination patterns, molecular structures and supramolecular associations in thiophosphonic acid derivatives have been reviewed by Haiduc [9]. Electrochemical behavior of dithiophosphonates is important from the point of view of determination in various samples.…”

Section: Introductionmentioning

confidence: 99%

Investigation of Electrochemical Behavior of Some Dithiophosphonates in Acetonitrile on the Platinum and Gold Electrodes

Çekirdek¹,

Solak²,

Karakuş³

et al. 2006

Electroanalysis

View full text Add to dashboard Cite

Some dithiophosphonate derivatives were synthesized and the electrochemical reduction mechanism was investigated by cyclic voltammetry (CV), square wave voltammetry (SWV) and chronoamperometry (CA) in 0.1 M tetrabutylammoniumtetrafluoroborate (TBATFB) in acetonitrile at platinum (Pt) and gold (Au) electrodes. Dithiophosphonates showed a cyclic voltammetric reduction peak at about À 1.1 V at Pt and À 1.3 V at Au electrode (vs. Ag/Ag þ ) in this media. It was also shown that dithiophosphonates can be determined quantitatively in acetonitrile using a calibration graph. The number of electrons transferred were calculated as 2 using ferrocene as a reference compound at the UME electrode. Mechanism of dithiophosphonates was also examined on Pt and Au electrodes and electrochemical reduction of dithiophosphonates seems to follow an EC mechanism with an irreversible electron transfer step. The reaction product in the bulk electrolysis experiment was isolated and identified using protoncoupled P-31 NMR, 13 C-NMR and IR spectroscopy. The adsorption tests for dithiophosphonates were revealed that no strong or weak adsorption phenomena exist on both Pt and Au electrodes. Simulation curves were acquired by DigiSim 3.03 version to investigate the reduction mechanism and to estimate the kinetic parameters for electrochemical and chemical steps.

show abstract

Spectroscopic and magnetic studies of some copper(II) and chromium(III) complexes with dithiophosphonates as ligands

Cited by 18 publications

References 11 publications

One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O₂/HO^–

One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O₂/HO^–

EPR and ESE of CuS4 complex in Cu(dmit)2: g-Factor and hyperfine splitting correlation in tetrahedral Cu–sulfur complexes

Investigation of Electrochemical Behavior of Some Dithiophosphonates in Acetonitrile on the Platinum and Gold Electrodes

Contact Info

Product

Resources

About

Spectroscopic and magnetic studies of some copper(II) and chromium(III) complexes with dithiophosphonates as ligands

Cited by 18 publications

References 11 publications

One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O2/HO–

One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O2/HO–

EPR and ESE of CuS4 complex in Cu(dmit)2: g-Factor and hyperfine splitting correlation in tetrahedral Cu–sulfur complexes

Investigation of Electrochemical Behavior of Some Dithiophosphonates in Acetonitrile on the Platinum and Gold Electrodes

Contact Info

Product

Resources

About

One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O₂/HO^–

One Electron Reduced Square Planar Bis(benzene-1,2-dithiolato) Copper Dianionic Complex and Redox Switch by O₂/HO^–