Thio-oxalates: their ligand properties and coordination chemistry

Dietzsch, W.; Strauch, Peter; Hoyer, Eberhard

doi:10.1016/0010-8545(92)80065-y

Cited by 56 publications

(43 citation statements)

References 216 publications

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“…Aside from crystal engineering studies, [M(dto) 2 ] 2− anions have been used as ligands in coordination chemistry. 11 In order to probe the robustness of the M(dto) • • • HN synthon D and its utility in diversifying the crystal structures it may be used to prepare, we have sought to synthesise salts of a range of [M(dto) 2 ] 2− dianions (M = Ni, Pt, Cu) with various molecular and supramolecular cations based on pyridinium and piperidinium derivatives.…”

Section: Introductionmentioning

confidence: 99%

Cation and anion diversity in [M(dithiooxalate)2]2? salts: structure robustness in crystal synthesis

et al. 2006

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A series of crystalline salts based on the [M(dto)2]2- (dto = 1,2-dithiooxalate, M = Ni, Pt, Cu) dianion with hydrogen-bond donor cations have been synthesised following a molecular tectonics approach. The chelating M(dto)[dot dot dot]HN supramolecular synthon has been exploited in a systematic study of its robustness. The effects of competition between hydrogen-bond acceptors, of the shape and functionality of the cations and of varying the metal in the anion are discussed. The preparation and structural characterisation of the new crystalline phases [4,4'-H(2)bipy][Pt(dto)2] (2), [HNC5H4CO2H-4]2[Pt(dto)2] (5), [HNC5H4CO2H-3]2[Pt(dto)2] (6), [HNC5H4CH2CO2H-4]2[Ni(dto)2] (7), [HNC(5)H(4)CH(2)CO(2)H-3]2[Ni(dto)2] (8), [HNC5H4CONH2-4]2[Ni(dto)2] (9), [HNC5H4CHNOH-4]2[Ni(dto)2] (10), [HNC5H4CHNOH-3]2[Ni(dto)2] (11), [4,4'-H2bipip][Ni(dto)2] (12), [H2NC5H9CO2H-4]2[Pt(dto)2] (12), [H2NC5H9CO2H-4]2[Cu(dto)2] (14), [H2NC5H9CO2H-3]2[Ni(dto)2][H2O]2 (15), [H2NC5H9CO2H-3]2[Pt(dto)2][H2O]2 (16), [H2NC5H9CO2H-3]2[Cu(dto)2][H2O]2 (17), [H(Me)NC5H9CO2H-4]2[Ni(dto)2][H2O]2 (18) is reported. The charge-assisted NH[dot dot dot]dto synthon is formed in each of compounds 1-20, and is apparently much more robust than the conventional synthons used (such as the carboxylic acid dimer), which have a much lower rate of occurrence. The NH[dot dot dot]dto synthon may be generalised to 3- and 4-pyridinium species and 3- and 4-piperidinium derivatives. In the latter cases branching of the hydrogen-bond networks through the NH2 groups arises. The robustness of the NH...dto synthon allows structures of the form [NH cation]2[M(dto)2] to be regarded as being formed by the packing of neutral supermolecules. Cases of isomorphism (as in 16-18) and latent polymorphism (e.g. in 4 and 6) are noted.

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Section: Introductionmentioning

confidence: 99%

Cation and anion diversity in [M(dithiooxalate)2]2? salts: structure robustness in crystal synthesis

et al. 2006

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“…[37] For example, 5 maleonitriledithiolate, [15Ϫ19] dithiooxalate [20,21] etc.) have shows a shoulder at 346 nm and a relatively strong and been studied photochemically so far.…”

Section: Introductionmentioning

confidence: 99%

Comparison of Electrochemically and Photochemically Induced Electron-Transfer Processes of a Series of Copper(II) Schiff Base Complexes with Thiolate Coordination

Knoblauch

Hartl²,

Stufkens

et al. 1999

Eur. J. Inorg. Chem.

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The electrochemical and photoredox properties of copper(II) thiopyrazolone Schiff base complexes 1–9 with imine and thiolate coordination, showing variable degrees of tetrahedral distortion, were investigated by means of combined electrochemical and spectroscopic techniques in the temperature range of 193–293 K. The cyclic voltammograms of 1–9 in butyronitrile revealed that the reduction and oxidation paths are strongly dependent on the geometry of the CuN2S2 moiety. Due to the strong delocalization of the singly occupied redox orbital (SOMO) the oxidations and reductions occur in a narrow potential range. The one‐electron‐reduced 1(r)–9(r) and oxidized 1(o)–9(o) products were electrogenerated and stabilized inside optically transparent thin‐layer electrochemical (OTTLE) cells at variable temperatures and could be characterized for the first time by UV/Vis spectroscopy. The reduced formal d10 copper(I) species absorb only weakly in the visible region. The oxidized products 1(o)–9(o) show several strong absorptions in the visible region due to the presence of formal d8 copper(III) species. The spectral information allowed assignment of the initial photoproducts. Irradiations in donor media such as THF or EtOH initially produces 1(r)–9(r). No photoreduction was observed in tBuOH which cannot liberate reducing Hα. The primary oxidized species 1(o)–9(o) were formed in chlorinated acceptor solvents (CHCl3) on UV irradation. Fast relaxation to the ground state prevents the photoredox reactions from CT or LF excited states.

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“…1,2 The utility of this ditopic ligand stems from the asymmetry of the two binding sites: mid-to-late transition metal ions bind preferentially to the soft sulfur-donor dithiolate, whereas Lewis acidic metal ions bind preferentially to the hard oxygendonor α-diketonate. 2 This has led to the assembly of numerous mixed-metal oligomers and coordination polymers by simply combining hard and soft metal ions with a dithioxalate salt in a one-pot reaction. [3][4][5][6] The majority of these studies have focussed on the structural topology of the metal ions, and the magnetic properties of the constituent metal ions linked by this ligand.…”

mentioning

confidence: 99%

“…The electron transfer chemistry, inherent to bis(dithiolene) compounds, does not exist in monometallic bis(dithioxalate) species such as [Ni(dto) 2 ] 2-. 2 This stems from the resonance stabilisation within the (dto) 2-ligand, between the dithiolate and diolate forms (Scheme 1). Prior to this work the only example of reversible one electron transfer chemistry using (dto) 2was [M{(dto)SnX 4 } 2 ] 2-(M = Ni, Pd, Pt; X = F, Cl).…”

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confidence: 99%

Molecular and electronic structure of the dithiooxalato radical ligand stabilised by rare earth coordination

et al. 2019

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Thio-oxalates: their ligand properties and coordination chemistry

Cited by 56 publications

References 216 publications

Cation and anion diversity in [M(dithiooxalate)2]2? salts: structure robustness in crystal synthesis

Cation and anion diversity in [M(dithiooxalate)2]2? salts: structure robustness in crystal synthesis

Comparison of Electrochemically and Photochemically Induced Electron-Transfer Processes of a Series of Copper(II) Schiff Base Complexes with Thiolate Coordination

Molecular and electronic structure of the dithiooxalato radical ligand stabilised by rare earth coordination

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