A Bio‐Inspired Switch Based on Cobalt(II) Disulfide/Cobalt(III) Thiolate Interconversion

Gennari, Marcello; Gerey, Bertrand; Hall, Nikita; Pécaut, Jacques; Collomb, Marie-Noëlle; Rouzières, Mathieu; Clérac, Rodolphe; Orio, Maylis; Duboc, Carole

doi:10.1002/ange.201402125

Cited by 13 publications

(5 citation statements)

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“… 15 Similarly, the group of Duboc recently reported a Co(III) thiolate compound that upon removal of chloride ions resulted in a Co(II) disulfide complex. 24 Clearly, the formation of metal thiolate or disulfide compounds cannot be predicted based on the anions only.…”

Section: Discussionmentioning

confidence: 99%

“…Combination of experimental results and DFT calculations confirm the formation of a low-spin ( S = 0) mononuclear Co(III)-thiolate compound in contrast to the dinuclear dithiolate-bridged structure reported for Cu(II) and the dinuclear Co(II) compounds with quartet-spin state (two S = 3/2 ions) reported by the group of Duboc. 18 , 24 The antiferromagnetic interaction between the two Cu(II) ions or the strong antiferromagnetic coupling between two S = 3/2 cobalt(II) ions reported by the group of Duboc are likely beneficial for the stabilization of the dinuclear compounds. Our computations show that antiferromagnetic coupling does not stabilize dinuclear cobalt(III) thiolate compounds 5 and 6 .…”

Section: Discussionmentioning

confidence: 99%

“…Duboc et al reported the electrochemical synthesis of a triplet-spin state ( S = 1) Co(III) thiolate compound and its redox interconversion to a Co(II) disulfide compound triggered by the removal of chloride ions. 24 Herein, we report a low-spin ( S = 0) Co(III) thiolate compound, which was formed directly from a reaction of a cobalt(II) salt with ligand di-2-(bis(2-pyridylmethyl)amino)-ethyl disulfide (L 1 SSL 1 ). The redox interconversion of this Co(III) thiolate compound and the related Co(II) disulfide compound has been investigated.…”

Section: Introductionmentioning

confidence: 99%

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Redox Interconversion between Cobalt(III) Thiolate and Cobalt(II) Disulfide Compounds

et al. 2018

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The redox interconversion between Co(III) thiolate and Co(II) disulfide compounds has been investigated experimentally and computationally. Reactions of cobalt(II) salts with disulfide ligand L1SSL1 (L1SSL1 = di-2-(bis(2-pyridylmethyl)amino)-ethyl disulfide) result in the formation of either the high-spin cobalt(II) disulfide compound [CoII2(L1SSL1)Cl4] or a low-spin, octahedral cobalt(III) thiolate compound, such as [CoIII(L1S)(MeCN)2](BF4)2. Addition of thiocyanate anions to a solution containing the latter compound yielded crystals of [CoIII(L1S)(NCS)2]. The addition of chloride ions to a solution of [CoIII(L1S)(MeCN)2](BF4)2 in acetonitrile results in conversion of the cobalt(III) thiolate compound to the cobalt(II) disulfide compound [CoII2(L1SSL1)Cl4], as monitored with UV–vis spectroscopy; subsequent addition of AgBF4 regenerates the Co(III) compound. Computational studies show that exchange by a chloride anion of the coordinated acetonitrile molecule or thiocyanate anion in compounds [CoIII(L1S)(MeCN)2]2+ and [CoIII(L1S)(NCS)2] induces a change in the character of the highest occupied molecular orbitals, showing a decrease of the contribution of the p orbital on sulfur and an increase of the d orbital on cobalt. As a comparison, the synthesis of iron compounds was undertaken. X-ray crystallography revealed that structure of the dinuclear iron(II) disulfide compound [FeII2(L1SSL1)Cl4] is different from that of cobalt(II) compound [CoII2(L1SSL1)Cl4]. In contrast to cobalt, reaction of ligand L1SSL1 with [Fe(MeCN)6](BF4)2 did not yield the expected Fe(III) thiolate compound. This work is an unprecedented example of redox interconversion between a high-spin Co(II) disulfide compound and a low-spin Co(III) thiolate compound triggered by the nature of the anion.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Redox Interconversion between Cobalt(III) Thiolate and Cobalt(II) Disulfide Compounds

et al. 2018

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“…They may originate from the reduction of the disulfide or metal-centered reduction based on the reported literature. The two irreversible anodic responses at E pa = 0.11 V and 0.27 V vs. Fc/Fc + are most likely due to the oxidation of the thiolate ligand [ 40 , 41 , 42 , 43 , 44 ].…”

Section: Resultsmentioning

confidence: 99%

Bimetallic Perthiocarbonate Complexes of Cobalt: Synthesis, Structure and Bonding

Pradhan,

Mishra,

Kaur

et al. 2024

Molecules

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The syntheses and structural elucidation of bimetallic thiolate complexes of early and late transition metals are described. Thermolysis of the bimetallic hydridoborate species [{Cp*CoPh}{µ-TePh}{µ-TeBH3-ĸ2Te,H}{Cp*Co}] (Cp* = ɳ5-C5Me5) (1) in the presence of CS2 afforded the bimetallic perthiocarbonate complex [(Cp*Co)2(μ-CS4-κ1S:κ2S′)(μ-S2-κ2S″:κ1S‴)] (2) and the dithiolene complex [(Cp*Co)(μ-C3S5-κ1S,S′] (3). Complex 2 contains a four-membered metallaheterocycle (Co2S2) comprising a perthiocarbonate [CS4]2− unit and a disulfide [S2]2− unit, attached opposite to each other. Complex 2 was characterized by employing different multinuclear NMR, infrared spectroscopy, mass spectrometry, and single-crystal X-ray diffraction studies. Preliminary studies show that [Cp*VCl2]3 (4) with an intermediate generated from CS2 and [LiBH4·THF] yielded thiolate species, albeit different from the cobalt system. Furthermore, a computational analysis was performed to provide insight into the bonding of this bimetallic perthiocarbonate complex.

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“…2 Besides this, the RSSR/RSH interconversion controlled by metal ion species is now found to play a mediate role in several relevant biochemical processes, including transportation of metal ions. 3 However, to the best of our knowledge, only a few investigations, limited to Cu(II), 4−11 Co(II) 12 and Mn(II) 12 ions, have been reported on metal ion-controlled interconversion.…”

Section: ■ Introductionmentioning

confidence: 99%

Palladium(II) Ion Mediated Disulfide/Thiolate Interconversion: Predicting the Disulfide Group State from First Principles

Петров

Dergachev

2019

J. Phys. Chem. A

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Different reactivity of homologous disulfides toward Pd2+ was previously reported: stepwise complexation to Pd2+ for l-cystine and cystamine ligands, while for dl-homocystine and 3,3′-dithiodipropionic acid, disulfide’s disproportionation toward thiolate and sulfinic acid complexes is observed. The disulfide/thiolate interconversion of four different disulfide ligands in the presence of nonredox metal cation Pd2+ in aqueous solution has been computationally investigated. We see this different reactivity in different capacities of considered homologous disulfides to stabilize forming S,S′-binuclear complexes, which are believed to be key intermediates toward interconversion products. We thus devise a theoretical model that rationalizes experimentally observed phenomenon of disulfides different reactivity toward nonredox transition metal cation Pd2+.

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A Bio‐Inspired Switch Based on Cobalt(II) Disulfide/Cobalt(III) Thiolate Interconversion

Cited by 13 publications

References 32 publications

Redox Interconversion between Cobalt(III) Thiolate and Cobalt(II) Disulfide Compounds

Redox Interconversion between Cobalt(III) Thiolate and Cobalt(II) Disulfide Compounds

Bimetallic Perthiocarbonate Complexes of Cobalt: Synthesis, Structure and Bonding

Palladium(II) Ion Mediated Disulfide/Thiolate Interconversion: Predicting the Disulfide Group State from First Principles

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