Die Kristallstruktur von Kaliumdithiooxalat

Mattes, R.; Meschede, Wolfgang; Stork, Wolfgang

doi:10.1002/cber.19751080102

Cited by 20 publications

(4 citation statements)

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“…In the three molecular structures, the C(1)–C(2) bond that connects the two [Mo 2 ] units decreases in length as the chelating O atoms are replaced by S atoms, being 1.508(2) Å for [ OO–OO ], 1.476(8) Å for [ OS–OS ], and 1.454(7) Å for [ SS–SS ]. Notably, these C–C bond distances are appreciably shorter than those in the acid or anion of the bridging ligands, for example, 1.544(5) Å in oxalic acid, 1.516(4) Å in K 2 dto, and 1.516(6) Å in (Et 4 N) 2 tto . The C–C bond contraction is consistent with increasing electron delocalization along the charge transfer axis.…”

Section: Resultsmentioning

confidence: 96%

“…The Mo−Mo bonds in the dimeric motif are lengthened as a result of introducing S atoms to the bridging ligands (see Table S2), in a manner similar to that found for the phenylene-bridged series, [Mo 2 ]−(μ-1,4-C 6 H 4 )−[Mo 2 ]. 35 For the same reason, the shortest (6.953(2) Å) and longest (7.881 Notably, these C−C bond distances are appreciably shorter than those in the acid or anion of the bridging ligands, for example, 1.544(5) Å in oxalic acid, 39 1.516(4) Å in K 2 dto, 40 and 1.516(6) Å in (Et 4 N) 2 tto. 41 The C−C bond contraction is consistent with increasing electron delocalization along the charge transfer axis.…”

Section: ■ Introductionmentioning

confidence: 99%

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Optical Behaviors and Electronic Properties of Mo₂–Mo₂ Mixed-Valence Complexes within or beyond the Class III Regime: Testing the Limits of the Two-State Model

et al. 2017

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Three symmetric Mo 2 dimers [Mo 2 (DAniF) 3 ](µ-E 2 CCE 2)[Mo 2 (DAniF) 3 ] (DAniF = N, Nʹ-di(p-anisyl)formamidinate) with oxalate (E = O) or the thiolated derivatives (E = O or S) as bridging ligands have been synthesized, and the optical properties of the mixed-valence (MV) derivatives obtained by one-electron oxidation studied within the framework of the vibronic two-state model. These Mo 2 −Mo 2 systems are effective models for testing electron transfer theories, with the δ electrons of the Mo 2 fragments that are responsible for the redox and optical properties of the MV complex being well isolated from other metal d and ligand π-type orbitals. This in turn gives rise to unique, well-resolved metal to ligand (MLCT) and intervalence charge transfer (IVCT) absorption bands that permit accurate analyses based on band-shape. In the series [Mo 2 (DAniF) 3 ](µ-E 2 CCE 2)[Mo 2 (DAniF) 3 ], the extent of electron delocalization between the Mo 2 cores increases with increasing number of sulfur atoms, E, in the bridge. Higher energy IVCT absorption bands are observed for the more strongly coupled complex, but in contrast to the predictions from the two-state model, the IVCT band becomes more symmetric in shape as the electronic coupling constant increases beyond the Class III border and 2H ab /λ >> 1. Thus, the oxalate-bridged complex (E 2 = O 2) is situated on the Class II-III borderline, while the two thiolated 2 species are well placed deep into Class III, where novel optical behavior can be observed. The electronic coupling matrix elements (H DA) estimated from the transition energy E IT (H DA = E IT /2, 2000-2500 cm − 1) are in excellent agreement with data (H ab , 2400-3000 cm − 1) calculated from the modified Mulliken-Hush expression for Class III systems. DFT calculations show that linear combinations of the δ orbitals of the Mo 2 centers generate the HOMO (out-of-phase, δ−δ) and HOMO-1 (in-phase, δ+δ), with the energy difference corresponding to the E IT. This study illustrates a systematic transition from strongly coupled MV complex near the Class II-III border, to Class III and to systems in which the underlying ground state is better described in terms of simple delocalized electronic states rather evolving from strongly coupled diabatic states which define Class III.

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Section: Resultsmentioning

confidence: 96%

Section: ■ Introductionmentioning

confidence: 99%

Optical Behaviors and Electronic Properties of Mo₂–Mo₂ Mixed-Valence Complexes within or beyond the Class III Regime: Testing the Limits of the Two-State Model

et al. 2017

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“…To our knowledge, such compounds with a CSSM (M = alkali metal) moiety in which the two C−S and S−M bond lengths differ (anisobidentate) are rare. In analogous compounds such as ionic potassium dithioacetate, dithiocarbamates 3a,b,11 dithioformate, 1,1-dithioxanthates, , and 1,1,2-trithiooxalate and dithiocarboxylato transition metal complexes PhCS 2 Re(CO) 4 , (CH 3 CS 2 ) 4 Mo, (PhCS 2 ) 4 Mo 2 (THF) 2 , (PhCS 2 ) 2 Ni, (PhCH 2 CS 2 ) 4 Pd 2 , and [4-( i -Pr)C 6 H 4 CS 2 ] 4 Pt 2 , without exception, the lengths of the two C−S and S−M bonds are equivalent in the chelated four-membered rings CSSM. This difference between the C−S bonds seems to indicate a slight localization of negative charge on the dithiocarboxylate group.…”

Section: Resultsmentioning

confidence: 99%

Heavy Alkali Metal Arenedithiocarboxylates: A Facile Synthesis, Dimeric Structure, and Nonbonding Interaction between the Metals and Aromatic Ring Carbons

et al. 1999

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Dithiocarboxylic acids and their trimethylsilyl esters were found to readily react with potassium, rubidium, and cesium fluorides to give the corresponding alkali metal dithiocarboxylates 3-5 in moderate to good yields. A series of tetramethylammonium dithiocarboxylates 8 have been prepared in good yields by the reaction of sodium dithiocarboxylates 7 with tetramethylammonium chloride. The structures of potassium (3b), rubidium (4g), cesium (5f), and tetramethylammonium 4-methylbenzenecarbodithioates (8e) and tetramethylammonium 2-methoxybenzenecarbodithioate (8f) were characterized crystallographically. These heavier alkali metal salts (3b, 4g, 5f) have a dimeric structure [(RCSSM)(2), M = K, Rb, Cs] in which the two dithiocarboxylate groups are chelated to the metal cations which are located on the upper and lower sides of the plane involving the two opposing dithiocarboxylate groups. The K(+) cations interact with the tolyl fragment of a neighboring molecule, while the Rb(+) and Cs(+) cations interact with two neighboring tolyl fragments, in which the ipso and ortho carbons are positioned close to the metals. The interaction number of the metals with surrounding atoms is 8 for K(+) and Rb(+) and 12 for Cs(+). The C-S distances of the dithiocarboxylate group are different for the potassium salt 3b. In contrast, those of the rubidium salt 4g and cesium salt 5f are equal. Similarly, the chelating sulfur-metal bond distances of 3b are different, while those of 4g and 5f are almost equal. The dihedral angles of the phenyl ring and dithiocarboxylate plane increase in the order of the K, Rb, and Cs salts. The structural analysis of sodium 4-methylbenzenecarbodithioate (7g) revealed the presence of 4-CH(3)C(6)H(4)CS(2)Na(0.36). In contrast, the tetramethylammonium salts 8 are monomeric where the cation moieties are located out of the dithiocarboxylate plane. The potassium 3, rubidium 4, and cesium dithiocarboxylates 5 readily reacted with methyl iodide or triorganotin chlorides at room temperature to give the corresponding methyl 9 and triorganotin dithioesters 10 in good yields. At 0 degrees C, the reactivity of the rubidium 4 and cesium salts 5 to methyl iodides decreases dramatically compared with those of the sodium salts 7 and potassium salts 3.

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“…The first report on the dithiooxalate anion (dto 2− ) and its phenyl dithiooxalate precursor dates back to 1909 when Jones and Tasker described the preparation of potassium dithiooxalate and the use of this anion as a ligand against nickel( ii ), palladium( ii ) and platinum( ii ) cations. 1 However, the X-ray structure of potassium dithiooxalate was not determined until 1975 by Mattes et al 2 Although the dithiooxalate ligand is quite stable, its partial hydrolytic decomposition into oxalate was observed in a few cases in the formation of metal complexes when using [Ni(dto) 2 ] 2− as a metalloligand against fully solvated metal ions such as calcium( ii ), 3 cerium( iii ), 4 lanthanum( iii ), and ytterbium( iii ). 5 Among the mononuclear complexes with dithiooxalate, 6 those containing the bis(dithiooxalato- κ 2 S , S′ )metallate( ii ) entity (M = Ni, Pd and Pt) have been the subject of various structural studies because of their stability in solution and the relative facility to grow X-ray quality crystals with this complex anion in the presence of metal and bulky countercations.…”

Section: Introductionmentioning

confidence: 99%

Bulky countercation effects on the crystal packing of anionic dithiooxalato-containing Ni(ii), Pd(ii) and Pt(ii) complexes: spectroscopic–redox correlations

et al. 2022

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Die Kristallstruktur von Kaliumdithiooxalat

Cited by 20 publications

References 13 publications

Optical Behaviors and Electronic Properties of Mo₂–Mo₂ Mixed-Valence Complexes within or beyond the Class III Regime: Testing the Limits of the Two-State Model

Optical Behaviors and Electronic Properties of Mo₂–Mo₂ Mixed-Valence Complexes within or beyond the Class III Regime: Testing the Limits of the Two-State Model

Heavy Alkali Metal Arenedithiocarboxylates: A Facile Synthesis, Dimeric Structure, and Nonbonding Interaction between the Metals and Aromatic Ring Carbons

Bulky countercation effects on the crystal packing of anionic dithiooxalato-containing Ni(ii), Pd(ii) and Pt(ii) complexes: spectroscopic–redox correlations

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Die Kristallstruktur von Kaliumdithiooxalat

Cited by 20 publications

References 13 publications

Optical Behaviors and Electronic Properties of Mo2–Mo2 Mixed-Valence Complexes within or beyond the Class III Regime: Testing the Limits of the Two-State Model

Optical Behaviors and Electronic Properties of Mo2–Mo2 Mixed-Valence Complexes within or beyond the Class III Regime: Testing the Limits of the Two-State Model

Heavy Alkali Metal Arenedithiocarboxylates: A Facile Synthesis, Dimeric Structure, and Nonbonding Interaction between the Metals and Aromatic Ring Carbons

Bulky countercation effects on the crystal packing of anionic dithiooxalato-containing Ni(ii), Pd(ii) and Pt(ii) complexes: spectroscopic–redox correlations

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Optical Behaviors and Electronic Properties of Mo₂–Mo₂ Mixed-Valence Complexes within or beyond the Class III Regime: Testing the Limits of the Two-State Model

Optical Behaviors and Electronic Properties of Mo₂–Mo₂ Mixed-Valence Complexes within or beyond the Class III Regime: Testing the Limits of the Two-State Model