Reversible S−S Bond Breaking and Bond Formation in Disulfide-Containing Dinuclear Complexes of MnI

Ruiz, Javier; Ceroni, Mario; Quinzani, Oscar V.; Piro, Oscar E.

doi:10.1002/1521-3773(20010105)40:1<220::aid-anie220>3.0.co;2-3

Cited by 14 publications

(1 citation statement)

References 11 publications

(14 reference statements)

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“…As expected, the cyclic voltammogram (CV) of 2c shows an irreversible oxidation at +0.12 V, ascribable to the generation of the cationic part of 4c. Correspondingly, the CV profile of 4c shows an irreversible reduction at −0.78 V, that could be assigned to the formation of 2c [61]. Further considerations are prevented due to the presence of iodide as the counteranion in 4c, which is redox active and leads to the deposition of degradation products on the surface of the working electrode.…”

Section: Electrochemistrymentioning

confidence: 97%

Mono-, Di- and Tetra-iron Complexes with Selenium or Sulphur Functionalized Vinyliminium Ligands: Synthesis, Structural Characterization and Antiproliferative Activity

Agonigi

Batchelor

Ferretti³

et al. 2020

Molecules

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A series of diiron/tetrairon compounds containing a S- or a Se-function (2a–d, 4a–d, 5a–b, 6), and the monoiron [FeCp(CO){SeC1(NMe2)C2HC3(Me)}] (3) were prepared from the diiron μ-vinyliminium precursors [Fe2Cp2(CO)( μ-CO){μ-η1: η3-C3(R’)C2HC1N(Me)(R)}]CF3SO3 (R = R’ = Me, 1a; R = 2,6-C6H3Me2 = Xyl, R’ = Ph, 1b; R = Xyl, R’ = CH2OH, 1c), via treatment with S8 or gray selenium. The new compounds were characterized by elemental analysis, IR and multinuclear NMR spectroscopy, and structural aspects were further elucidated by DFT calculations. The unprecedented metallacyclic structure of 3 was ascertained by single crystal X-ray diffraction. The air-stable compounds (3, 4a–d, 5a–b, 6) display fair to good stability in aqueous media, and thus were assessed for their cytotoxic activity towards A2780, A2780cisR, and HEK-293 cell lines. Cyclic voltammetry, ROS production and NADH oxidation studies were carried out on selected compounds to give insights into their mode of action.

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Section: Electrochemistrymentioning

confidence: 97%

Mono-, Di- and Tetra-iron Complexes with Selenium or Sulphur Functionalized Vinyliminium Ligands: Synthesis, Structural Characterization and Antiproliferative Activity

Agonigi

Batchelor

Ferretti³

et al. 2020

Molecules

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New Approach to the Chemistry of Polysulfides Using Diphosphanylmethanide Complexes of Manganese(I)

Ruiz¹,

Ceroni²,

Quinzani³

et al. 2001

Chem. Eur. J.

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The study of the nucleophilic degradation of S8 by the methanide complex [Mn(CO)4[(PPh2)2CH]] (2) has led to the preparation of a unique class of polysulfide derivatives of formula [(CO)4Mn[(PPh2)2C-Sn-C(PPh2)2]-Mn(CO)4]. The structures of 3 (n = 6), 4 (n = 2), and 7 (n = 1) have been determined by X-ray crystallography, whereas those polysulfides with the sulfur chains S7, S5, S4, and S3 have been detected by spectroscopic methods. The polysulfides with n > 2 lose sulfur spontaneously, a process that can be accelerated by treatment with PPh3 or Na/Hg. Complexes 3, 4, and 7 were protonated at the two methanide carbon atoms to give the cationic dinuclear derivatives [(CO)4Mn[(PPh2)2C(H)-Sn-C(H)-(PPh2)2]Mn(CO)4]2+ (8, n=6; 9, n=2; 10, n = 1). The 1H NMR spectrum of 9 suggests the existence of intramolecular C-H...S interactions, in agreement with the X-ray structural determination of this complex. By treatment of 4 and 7 with one equivalent of HBF4 it is possible to selectively protonate just one methanide carbon atom, which allows the isolation of the mixed cationic derivatives R(CO)4Mn[(PPh2)2C(H)-Sn-C(PPh2)2]Mn(CO)4]+ (11, n = 2; 6, n = 1). Additionally, heterometallic complexes containing a bridging disulfide unit, of general formula [(CO)4Mn[(PPh2)2C(AuPPh3)S-SC-(AuPPh3)(PPh2)2]Mn(CO)4]2+ (12) and [(CO)4Mn[(PPh2)2C(H)S-SC(AuPPh3)-(PPh2)2]Mn(CO)4]+ (13), were prepared by reaction of 4 and 11, respectively, with [AuCl(PPh3)] in the presence of TlPF6.

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Insertion of Thiocyanogen into a PC Bond and Subsequent Formation of Polysulfide Derivatives

et al. 2003

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Reversible S−S Bond Breaking and Bond Formation in Disulfide-Containing Dinuclear Complexes of MnI

Cited by 14 publications

References 11 publications

Mono-, Di- and Tetra-iron Complexes with Selenium or Sulphur Functionalized Vinyliminium Ligands: Synthesis, Structural Characterization and Antiproliferative Activity

Mono-, Di- and Tetra-iron Complexes with Selenium or Sulphur Functionalized Vinyliminium Ligands: Synthesis, Structural Characterization and Antiproliferative Activity

New Approach to the Chemistry of Polysulfides Using Diphosphanylmethanide Complexes of Manganese(I)

Insertion of Thiocyanogen into a PC Bond and Subsequent Formation of Polysulfide Derivatives

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