Bis(1,3-dithiole-2-one-4,5-dithiolato)antimonate(1-) salts, [Q][Sb(dmio)2]. Structural comparisons of [Q][Sb(dmio)2] and bis(1,3-dithiole-2-thione-4,5-dithiolato)antimonate(1-) salts, [Q][Sb(dmit)2]

Aupers, John H.; Chohan, Zahid H.; Comerlato, Nadia M.; Howie, R. Α.; Silvino, Alexandre Carneiro; Wardell, Jámes L.; Wardell, Solange M. S. V.

doi:10.1016/s0277-5387(02)01156-7

Cited by 15 publications

(14 citation statements)

References 26 publications

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“…[10][11][12] The bands at 993, 895 and 881 cm -1 are assigned as C-S stretches. At 524 cm -1 , the breathing mode of the dmit ligant was observed.…”

Section: [Sb(dmit) 2 ] -1 Experimental Frequenciesmentioning

confidence: 99%

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] For instance, D 2d symmetry is present in Cu(II) and Zn(II) complexes, D 2h symmetry in Ni(II) complexes and C 2 symmetry for complexes of the Group 15 elements, Sb and Bi, in their trivalent oxidation state.…”

Section: Introductionmentioning

confidence: 99%

“…All the crystal structures of these complexes are known, [6][7][8][9][10][11][12][13][14][15] including those of the tetraethylammonium salts, a family showing an increasing degree of inter-anion interactions from the Zn to Bi complex. Therefore we could assess M-S inter-anion interactions in the solid state, by carefully comparing the gas-phase calculation to the solid-state bulk spectra of these systems.…”

Section: Introductionmentioning

confidence: 99%

“…The situation is different in the case of the anions in [10][11][12] or Bi [13][14][15] ): here there are metalsulfur inter-anion interactions, that raise the coordination number of the metal to 6, and that including the lone pair on the metal, provide highly distorted pseudo pentagonal bipyramidal geometries for Sb and Bi. While the cation, Q + , in each of the series, influences the anion arrangements and also the very weak S---S inter-anion interactions, the basic geometries about each of the two metals remain unaffected.…”

Section: Introductionmentioning

confidence: 99%

“…These three bands, also present in the infrared/Raman spectra of [Q] 2 [Zn(dmit) 2 ], have been used to confirm the presence of the dmit group in such complexes. [10][11][12] The bands at 993, 895 and 881 cm -1 are assigned as C-S stretches. At 524 cm -1 , the breathing mode of the dmit ligant was observed.…”

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confidence: 99%

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Vibrational spectra of bis(dmit) complexes of main group metals: IR, Raman and ab initio calculations

Ferreira¹,

Comerlato²,

Wardell³

et al. 2004

J. Braz. Chem. Soc.

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Este trabalho apresenta uma investigação teórico-experimental dos espectros infravermelho/ Raman de diversos metais representativos coordenados com 1,3-ditiol-2-tiona-4,5-ditiolato (dmit), a saber [NEt 4 . Os espectros IV/Raman de todos os sólidos e também o espectro IV em solução do composto [NEt 4 ] 2 [Zn(dmit) 2 ] foram registrados de 4000 a 100 cm -1 . Duas regiões foram claramente identificadas: abaixo de 380 cm -1 os modos apresentaram forte contribuição metal-ligante, e acima, os modos indicaram majoritária contribuição do ligante. Os espectros IV/Raman do NEt 4 Br também foram registrados. As bandas vibracionais foram atribuídas a partir da análise de compostos relacionados, de publicações prévias e comparadas com amplo conjunto de cálculos ab initio realizados com diversos ECPs (SBK, Sttutgart), conjunto de bases (com e sem funções d) e metodologias (RHF, DFT e MP2). As geometrias, freqüências e intensidades foram calculadas e comparadas com as freqüências experimentais visando atribuições seguras. Assim, uma excelente concordância foi obtida para diversas bandas experimentais.This work reports a theoretical-experimental investigation of the infrared/Raman vibrational spectra of several metal 1,3-dithole-2-thione-4,5-dithiolate (dmit) complexes; [NEt 4 2 ] were recorded from 4000 to 100 cm -1 . Two regions were clearly identified: below 380 cm -1 , the modes presented significant metal-ligand contributions, and above, the modes indicated major ligand contributions. IR/Raman spectra of NEt 4 Br have also been recorded. The vibrational bands have been assigned starting from the analysis of related compounds, of previous published spectra and compared to several ECPs (SBK, Stuttgart), basis sets (with and without functions d) and methodologies (RHF, MP2 and DFT). Geometries, frequencies and intensities were calculated and compared to the experimental frequencies seeking secure assignment. Thus, an excellent agreement was obtained for several experimental bands.Keywords: IR, Raman, ab initio, RHF, DFT, MP2, dmit complexes, Zn, Sb, Bi IntroductionThe syntheses and properties of metal complexes with 1,2-dithiolato-polysulfido ligands have been intensely studied 1-3 particularly since the discovery, by Cassoux and co-workers 4 in 1986, of the first metallic molecular superconductor, [TTF][Ni(dmit) 2 ] 2 , where dmit is the 1,3-dithiole-2-thione-4,5-dithiolate ligand. Presently dmit ligand complexes are the best studied.The publication of Cassoux and co-workers 4 seminal paper led a new impetus for the study of the applications of metal dmit compounds as super-conducting complexes, materials with non-linear optical properties and materials for electronic molecular devices. Such properties arise in part, from the rich redox chemistry of these compounds and the large polarizability of sulfur atoms.An additional important feature for the super-conducting property on metal bis(dmit) complexes, such as [TTF][Ni(dmit) 2 ] 2 , is the planar geometry of the anions, [3][4][5] dmit 2- Despite the large volume of wo...

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“…[10][11][12] The bands at 993, 895 and 881 cm -1 are assigned as C-S stretches. At 524 cm -1 , the breathing mode of the dmit ligant was observed.…”

Section: [Sb(dmit) 2 ] -1 Experimental Frequenciesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Vibrational spectra of bis(dmit) complexes of main group metals: IR, Raman and ab initio calculations

Ferreira¹,

Comerlato²,

Wardell³

et al. 2004

J. Braz. Chem. Soc.

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Heteroleptic dmit nickel complexes with bis(diphenylphosphanyl)amine ligands as robust molecular electrocatalysts for hydrogen evolution

Xie

Cao

et al. 2020

Applied Organom Chemis

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Four new neutral heteroleptic dmit nickel complexes bearing bis(diphenylphosphanyl)amine ligands, [RN (PPh 2) 2 Ni(dmit)] (where dmit 2− = 1,-3-dithiole-2-thione-4,5-dithiolate; R = (CH 2) 4 CH 3 [1], (CH 2) 3 OCH 3 [2], (CH 2) 2 CH (CH 3) 2 [3], and CHPhCH 3 [4]), have been synthesized in moderated yields by the reactions between (n-Bu) 2 Sn(dmit) and RN (PPh 2) 2 NiCl 2 at room temperature. The complexes were fully characterized by elemental analysis, spectroscopy (Fourier transform infrared [FTIR], ultraviolet-visible [UV-vis], 1 H, 13 C{ 1 H}, and 31 P{ 1 H} nuclear magnetic resonance [NMR]), thermogravimetric analysis, and single crystal X-ray diffraction. In the crystal structures of 1-3 and 4Á2CH 2 Cl 2 , every nickel atom adopts a slightly distorted square-planar coordination by two phosphorus atoms of the RN (PPh 2) 2 ligand and two sulfur atoms of the dmit ligand. Furthermore, the electrochemical behaviors and electrocatalytic activities of 1-4 for hydrogen evolution have also been investigated by the cyclic voltammetry using trifluoroacetic acid (TFA) as the proton source. With the addition of 120-mM trifluoroacetic acid to 0.5-mM 1-4 in MeCN, the turnover frequency values of these catalysts were estimated to be 2827-5149 s −1 , and the relevant overpotentials were 0.72-0.79 V. Density functional theory (DFT) calculations and electrochemical investigations suggest that H 2 production proceeds via a key hydride intermediate [NiH (SH)] with an adjacent protonated sulfur atom of the dmit ligand in which the chelating sulfur atoms serve as proton relays. These findings demonstrate that these heteroleptic dmit nickel complexes could serve as robust and effective molecular electrocatalysts for hydrogen evolution.

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Arsenic, Antimony and Bismuth

Coughlin¹,

Benjamin²

2021

Comprehensive Coordination Chemistry III

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Bis(1,3-dithiole-2-one-4,5-dithiolato)antimonate(1-) salts, [Q][Sb(dmio)2]. Structural comparisons of [Q][Sb(dmio)2] and bis(1,3-dithiole-2-thione-4,5-dithiolato)antimonate(1-) salts, [Q][Sb(dmit)2]

Cited by 15 publications

References 26 publications

Vibrational spectra of bis(dmit) complexes of main group metals: IR, Raman and ab initio calculations

Vibrational spectra of bis(dmit) complexes of main group metals: IR, Raman and ab initio calculations

Heteroleptic dmit nickel complexes with bis(diphenylphosphanyl)amine ligands as robust molecular electrocatalysts for hydrogen evolution

Arsenic, Antimony and Bismuth

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