An Alternate Route to Disulfanido Complexes by Nucleophilic Attack of Thiolates on Ruthenium-Bound Thiosulfonato Ligands

Galardon, Erwan; Deschamps, P; Tomas, Α.; Roussel, Pascal; Artaud, Isabelle

doi:10.1021/ic101795s

Cited by 7 publications

(10 citation statements)

References 24 publications

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“…[( p-Cymene)Ru(bipy)Cl]•PF 6 and [( p-cymene)Ru(en)Cl]•PF 6 were prepared from the corresponding chloro derivatives by anion exchange with NH 4 PF 6 in methanol. 1,5 The isotopically labeled 34 S phenylthiosulfonate was synthesized by the reaction of the sodium salt of phenylsulfinic acid with elemental sulfur (resp. 34 S) in pyridine.…”

Section: Methodsmentioning

confidence: 99%

“…For our studies, we used complexes (see Scheme 1) based on 2-2′-bipyridine (bipy), 1 as well as new complexes based on ethylenediamine (en).…”

Section: Synthesis and Characterization Of The Thiosulfonato Complexe...mentioning

confidence: 99%

“…The ruthenium-sulfur bond is slightly longer than in the ] + (0.019 and 0.034 Å, respectively) but within the range of that observed in the parent bipyridine complex 1b. 1 The difference of electronic properties between the pure σ-donor ethylenediamine and the π-acceptor 2-2′-bipyridine in 1b, which can compete with the arene for the ruthenium electronic density, is illustrated by the slightly longer ruthenium-arene centroid ring distance in the former than in the latter (Δ = 0.012 Å). The crystal structure also confirms that the ethylenediamine ligand can act as a hydrogen-bond donor in arene-ruthenium complexes, 13,14 with an N1-H1B⋯O1-S1 interaction indicated by the N1-O1 distance of 2.880 Å, which correlates with a longer S1-O1 than an S1-O2 bond.…”

Section: Synthesis and Characterization Of The Thiosulfonato Complexe...mentioning

confidence: 99%

“…However, the outcome of the reaction is strongly dependent on the diamine ligand. The product isolated from the reaction with 1a after precipitation with sodium tetraphenylborate shows a strongly shielded signal at −2.51 ppm in 1 H NMR integrating for one proton (Fig. S1 †).…”

Section: Reactivity Of Complexes 1 and 1′ With Hydrosulfidementioning

confidence: 99%

“…We have recently reported an original route towards these disulfanido complexes by nucleophilic attack of thiolates on ruthenium-bound thiosulfonato ligands. 1 In this reaction, the ruthenium(II) centre is crucial, as its kinetic inertness drives the reaction towards the S-SO 2 bond rather than towards the metal centre, resulting in the cleavage of the thiosulfonate and the formation of a new S-S bond. Here, we report the study of this reaction carried out with the hydrosulfide anion (HS − ).…”

Section: Introductionmentioning

confidence: 99%

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Influence of the diamine on the reactivity of thiosulfonato ruthenium complexes with hydrosulfide (HS⁻)

et al. 2013

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We have recently reported that cationic thiosulfonato ruthenium complexes [(p-cymene)Ru(bipy)(SSO(2)Ar)](+) (bipy: 2-2'-bipyridine, Ar: phenyl or p-tolyl) react with thiolates (RS(-), R = alkyl or aryl) by cleavage of the S-SO(2) bond and formation of a new S-S bond. In this work, we report that the outcome of the reaction is different if the hydrosulfide anion (R = H) is used, the product obtained being the hydrogen(sulfido) derivative [(p-cymene)Ru(bipy)(SH)](+). The bipy ligand is crucial in this result, and its replacement by ethylenediamine leads to a different product, the trisulfido-bridged dinuclear complex [[(p-cymene)Ru(en)(S)](2)S](2+). These two new species have been fully characterized, including by X-ray diffraction studies, and the two different mechanisms leading to their formation are discussed.

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Section: Methodsmentioning

confidence: 99%

“…For our studies, we used complexes (see Scheme 1) based on 2-2′-bipyridine (bipy), 1 as well as new complexes based on ethylenediamine (en).…”

Section: Synthesis and Characterization Of The Thiosulfonato Complexe...mentioning

confidence: 99%

Section: Synthesis and Characterization Of The Thiosulfonato Complexe...mentioning

confidence: 99%

Section: Reactivity Of Complexes 1 and 1′ With Hydrosulfidementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Influence of the diamine on the reactivity of thiosulfonato ruthenium complexes with hydrosulfide (HS⁻)

et al. 2013

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Reactivity of Zinc Thiolate Bonds: Oxidative Organopolysulfide Formation and S₃ Insertion

Ballesteros

Tsui

2019

Inorg. Chem.

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Zinc thiolate bonds are intriguing targets of study because of their redox noninnocence and prevalence in bioinorganic sites. A five-coordinate zinc dithiolate complex [Et4N]2[LZn] (H4L = N,N′-di(2-sulfhydrylphenyl)-pyridine-2,6-dicarboxamide) was synthesized to study the oxidative reactivity of zinc thiolate bonds. Multiple chemically reversible reactions of the zinc thiolate bonds were identified. Oxidation of [Et4N]2[LZn] with iodine resulted in structural rearrangement to a bimetallic disulfide-bridged complex. In contrast, the addition of elemental sulfur to [Et4N]2[LZn] resulted in the insertion of a neutral S3 fragment into the Zn–thiolate bond to selectively form an unusual monometallic tetrasulfanido complex. When oxidized, this tetrasulfanido compound rearranged to form a bimetallic trisulfide-bridged complex. The observed diversity of zinc thiolate reactivity, particularly with sulfur, is likely important in biological contexts.

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Synthesis, Characterization, and Reactivity of a Synthetic End-On Cobalt(II) Alkyl Persulfide Complex as a Model Platform for Thiolate Persulfidation

Li,

Zakharov,

Pluth

2024

J. Am. Chem. Soc.

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Persulfides (RSS − ) are ubiquitous source of sulfides (S 2− ) in biology, and interactions between RSS − and bioinorganic metal centers play critical roles in biological hydrogen sulfide (H 2 S) biogenesis, signaling, and catabolism. Here, we report the use of contact-ion stabilized [Na(15-crown-5)][ t BuSS] (1) as a simple synthon to access rare metal alkyl persulfide complexes and to investigate the reactivity of RSS − with transition metal centers to provide insights into metal thiolate persulfidation, including the fundamental difference between alkyl persulfides and alkyl thiolates. Reaction of 1 with [Co II (TPA)(OTf)] + afforded the η 1 -alkyl persulfide complex [Co II (TPA)(SS t Bu)] + (2), which was characterized by X-ray crystallography, UV−vis spectroscopy, and Raman spectroscopy. RSS − coordination to the Lewis acidic Co 2+ center provided additional stability to the S−S bond, as evidenced by a significant increase in the Raman stretching frequency for 2 (v S−S = 522 cm −1 , Δv S−S = 66 cm −1 ). The effect of persulfidation on metal center redox potentials was further elucidated using cyclic voltammetry, in which the Co 2+ → Co 3+ oxidation potential of 2 (E p,a = +89 mV vs SCE) is lowered by nearly 700 mV when compared to the corresponding thiolate complex [Co II (TPA)(S t Bu)] + (3) (E p,a = +818 mV vs SCE), despite persulfidation being generally seen as an oxidative post-translational modification. The reactivity of 2 toward reducing agents including PPh 3 , BH 4 − , and biologically relevant thiol reductant DTT led to different S 2− output pathways, including formation of a dinuclear 2Co−2SH complex [Co II 2 (TPA) 2 (μ 2 -SH) 2 ] 2+ (4).

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An Alternate Route to Disulfanido Complexes by Nucleophilic Attack of Thiolates on Ruthenium-Bound Thiosulfonato Ligands

Cited by 7 publications

References 24 publications

Influence of the diamine on the reactivity of thiosulfonato ruthenium complexes with hydrosulfide (HS⁻)

Influence of the diamine on the reactivity of thiosulfonato ruthenium complexes with hydrosulfide (HS⁻)

Reactivity of Zinc Thiolate Bonds: Oxidative Organopolysulfide Formation and S₃ Insertion

Synthesis, Characterization, and Reactivity of a Synthetic End-On Cobalt(II) Alkyl Persulfide Complex as a Model Platform for Thiolate Persulfidation

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An Alternate Route to Disulfanido Complexes by Nucleophilic Attack of Thiolates on Ruthenium-Bound Thiosulfonato Ligands

Cited by 7 publications

References 24 publications

Influence of the diamine on the reactivity of thiosulfonato ruthenium complexes with hydrosulfide (HS−)

Influence of the diamine on the reactivity of thiosulfonato ruthenium complexes with hydrosulfide (HS−)

Reactivity of Zinc Thiolate Bonds: Oxidative Organopolysulfide Formation and S3 Insertion

Synthesis, Characterization, and Reactivity of a Synthetic End-On Cobalt(II) Alkyl Persulfide Complex as a Model Platform for Thiolate Persulfidation

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Product

Resources

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Influence of the diamine on the reactivity of thiosulfonato ruthenium complexes with hydrosulfide (HS⁻)

Influence of the diamine on the reactivity of thiosulfonato ruthenium complexes with hydrosulfide (HS⁻)

Reactivity of Zinc Thiolate Bonds: Oxidative Organopolysulfide Formation and S₃ Insertion