Sulfur transfer reactions of a zinc tetrasulfanido complex

Ballesteros, Moises; Tsui, Emily Y.

doi:10.1039/d0dt01384f

Cited by 7 publications

(8 citation statements)

References 39 publications

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“…Encouraged by our recent report on [Zn II ]-promoted thiol persulfidation through thiol and sulfane sulfur cross-talk, we aim to utilize the in situ generated persulfide species for facilitating NO generation from [( Bn 3 Tren )Zn II –nitrite] + ( 1 ). Notably, the insertion of the S 3 moiety into the [Zn II ]–SAr bond, resulting in the [Zn II ]–S 4 Ar complex, has been reported previously. , A comparative reactivity study on the structurally characterized [Zn II ]–SAr and [Zn II ]–S 4 Ar complexes toward alkylation and disulfide addition reactions demonstrates that [Zn II ]–S 4 Ar is less nucleophilic as compared to [Zn II ]–SAr . Thus, this study by Tsui and coworkers illustrated an inverse α-effect in thiolate versus perthiolate reactivity at a [Zn II ] site supported by a bis(carboxamide)pyridine ligand.…”

Section: Resultssupporting

confidence: 72%

“…Notably, the insertion of the S 3 moiety into the [Zn II ]–SAr bond, resulting in the [Zn II ]–S 4 Ar complex, has been reported previously. 37 , 38 A comparative reactivity study on the structurally characterized [Zn II ]–SAr and [Zn II ]–S 4 Ar complexes toward alkylation and disulfide addition reactions demonstrates that [Zn II ]–S 4 Ar is less nucleophilic as compared to [Zn II ]–SAr. 39 Thus, this study by Tsui and coworkers illustrated an inverse α-effect in thiolate versus perthiolate reactivity at a [Zn II ] site supported by a bis(carboxamide)pyridine ligand.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

NO Generation from Nitrite at Zinc(II): Role of Thiol Persulfidation in the Presence of Sulfane Sulfur

Sahana,

Valappil,

Amma

et al. 2023

ACS Org. Inorg. Au

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Nitrite-to-NO transformation is of prime importance due to its relevance in mammalian physiology. Although such a one-electron reductive transformation at various redox-active metal sites (e.g., Cu and Fe) has been illustrated previously, the reaction at the [Zn II ] site in the presence of a sacrificial reductant like thiol has been reported to be sluggish and poorly understood. Reactivity of [(Bn 3 Tren)Zn II −ONO](ClO 4 ) (1), a nitrite-bound model of the tripodal active site of carbonic anhydrase (CA), toward various organic probes, such as 4-tert-butylbenzylthiol ( t BuBnSH), 2,4-di-tert-butylphenol (2,4-DTBP), and 1-fluoro-2,4-dinitrobenzene (F-DNB), reveals that the ONO-moiety in the [Zn II ]−nitrite coordination motif of complex 1 acts as a mild electrophile. t BuBnSH reacts mildly with nitrite at a [Zn II ] site to provide S-nitrosothiol t BuBnSNO prior to the release of NO in 10% yield, whereas the phenolic substrate 2,4-DTBP does not yield the analogous O-nitrite compound (ArONO). The presence of sulfane sulfur (S 0 ) species such as elemental sulfur (S 8 ) and organic polysulfides ( t BuBnS n Bn t Bu) during the reaction of t BuBnSH and [Zn II ]−nitrite (1) assists the nitrite-to-NO conversion to provide NO yields of 65% (for S 8 ) and 76% (for t BuBnS n Bn t Bu). High-resolution mass spectrometry (HRMS) analyses on the reaction of [Zn II ]−nitrite (1), t BuBnSH, and S 8 depict the formation of zinc(II)-persulfide species [(Bn 3 Tren)Zn II −S n −Bn t Bu] + (where n = 2, 3, 4, 5, and 6). Trapping of the persulfide species ( t BuBnSS − ) with 1-fluoro-2,4-dinitrobenzene (F-DNB) confirms its intermediacy. The significantly higher nucleophilicity of persulfide species (relative to thiol/thiolate) is proposed to facilitate the reaction with the mildly electrophilic [Zn II ]−nitrite (1) complex. Complementary analyses, including multinuclear NMR, electrospray ionization-MS, UV−vis, and trapping of reactive S-species, provide mechanistic insights into the sulfane sulfur-assisted reactions between thiol and nitrite at the tripodal [Zn II ]-site. These findings suggest the critical influential roles of various reactive sulfur species, such as sulfane sulfur and persulfides, in the nitrite-to-NO conversion.

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Section: Resultssupporting

confidence: 72%

Section: Resultsmentioning

confidence: 99%

NO Generation from Nitrite at Zinc(II): Role of Thiol Persulfidation in the Presence of Sulfane Sulfur

Sahana,

Valappil,

Amma

et al. 2023

ACS Org. Inorg. Au

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“…This study used a pentadentate bis(carboxamide)pyridine-type ligand with pendant thiophenoxide donors, which provided two thiolate donations to the central five-coordinate Zn(II) ion. A S transfer reaction of this zinc(II) tetrasulfanido complex to dimethyl acetylenedicarboxylate was also reported recently . Another related study describes a zinc(II) alkylpersulfido complex, which was synthesized by the reaction of a tris(pyrazolyl)borate zinc(II) hydroxide complex with an alkyl hydrodisulfide reagent .…”

Section: Introductionmentioning

confidence: 79%

“…A S transfer reaction of this zinc(II) tetrasulfanido complex to dimethyl acetylenedicarboxylate was also reported recently. 78 Another related study describes a zinc(II) alkylpersulfido complex, which was synthesized by the reaction of a tris(pyrazolyl)borate zinc(II) hydroxide complex with an alkyl hydrodisulfide reagent. 15 Very recently, we reported an initial account for the synthesis and reactivity of two binuclear zinc(II) thiolate complexes, [Zn 2 (N-Et-HPTB)(μ 2 -SR)] 2+ (R = Et, C 6 H 4 -p-OMe), where N-Et-HPTB − is the anion of N,N,N′,N′-tetrakis [2-(1-ethylbenzimidazolyl)]-2-hydroxy-1,3diaminopropane.…”

Section: ■ Introductionmentioning

confidence: 99%

Polysulfido Chain in Binuclear Zinc(II) Complexes

Hossain

Majumdar

2022

Inorg. Chem.

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The synthesis and a detailed reactivity study of a binuclear zinc(II) bis(benzenethiolate) complex, [Zn 2 (BPMP)(SPh) 2 ] + (4), and an unprecedented binuclear zinc(II) pentasulfido complex, [Zn 2 (BPMP)(μ 2 -S 5 )] + (6), are presented. While one-electron oxidation of the coordinated benzenethiolate ligands in 4 by Cp 2 Fe + produces diphenyl disulfide and [Zn 2 (BPMP)(μ 2 -OH)] 2+ (5), a two-electron redox reaction between coordinated benzenethiolate ligands in 4 and elemental S (S 8 ) generated diphenyl disulfide and the binuclear zinc(II) pentasulfido complex 6. Complex 6 features a chelating, dianionic, pentasulfido (S 5 2− ) chain and can consume up to a maximum of 3 equiv of PPh 3 to generate Ph 3 PS and 5, while the reaction of 6 with 1 equiv of diphenylphosphinoethane allowed the isolation of [Zn 2 (BPMP)(μ 2 -S 4 )] + (7). A proteolysis reaction of the coordinated S 5 2− chain in 6 with fluoroboric acid (HBF 4 ), benzoic acid (PhCOOH), and thioacetic acid (MeCOSH) generates the complexes [Zn 2 (BPMP)(MeCN) 2 ] 3+ (1), [Zn 2 (BPMP)(μ 2 -PhCOO) 2 ] + (8), and [Zn 2 (BPMP)(μ 2 -SCOMe) 2 ] + (9), respectively, while the protonated S 5 2− chain liberates S 8 and hydrogen sulfide (H 2 S). Finally, the transfer of the coordinated benzenethiolate ligands in 4 and the S 5 2− chain in 6 to selected organic compounds, namely, PhCH 2 Br and PhC(O)Cl, for the generation of various organosulfur compounds is demonstrated.

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“…While this Zn( ii )–tetrasulfanido complex could undergo similar reactions such as reactions with phosphines and with dimethyl acetylenedicarboxylate as transition metal–polysulfido complexes, the final products were quite different. 259 Recently, Tsui and coworkers have also demonstrated that polysulfanide anions are much less basic and exhibit less nucleophilicity than thiolates. 260…”

Section: Nonheme Binuclear Transition Metal–polychalcogenido Complexesmentioning

confidence: 99%

Nonheme binuclear transition metal complexes with hydrosulfide and polychalcogenides

Hossain,

Atta,

Chakraborty

et al. 2024

Chem. Commun.

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Sulfur transfer reactions of a zinc tetrasulfanido complex

Abstract: The sulfur transfer reactions of a zinc tetrasulfanido complex are explored and contrasted with those of metal polysulfidos.

Cited by 7 publications

References 39 publications

NO Generation from Nitrite at Zinc(II): Role of Thiol Persulfidation in the Presence of Sulfane Sulfur

NO Generation from Nitrite at Zinc(II): Role of Thiol Persulfidation in the Presence of Sulfane Sulfur

Polysulfido Chain in Binuclear Zinc(II) Complexes

Nonheme binuclear transition metal complexes with hydrosulfide and polychalcogenides

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