Synthesis and Structures of Cuprous Triptycylthiolate Complexes

Ferrara, Skylar J.; Mague, Joel T.; Donahue, James P.

doi:10.1021/ic300124n

Cited by 18 publications

(13 citation statements)

References 85 publications

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“…An alternative explanation of the nature and properties of the observed transients provides the possibility that IM1 and IM2 identify with Cu(I)–thiolates rather than with Cu(I) disulfides. As Cu(I)–thiolates can also form binuclear or polynuclear complexes [ 105 , 106 , 107 , 108 , 109 ], this alternative hypothesis could explain the proposed catalytic activity of IM1 and IM2 in a similar way as the disulfide hypothesis. As mentioned above, such intermediates have been proposed as possible oxidation catalysts [ 34 , 37 ].…”

Section: Discussionmentioning

confidence: 99%

Reaction of N-Acetylcysteine with Cu2+: Appearance of Intermediates with High Free Radical Scavenging Activity: Implications for Anti-/Pro-Oxidant Properties of Thiols

Valent

Bednářová

Schreiber

et al. 2022

IJMS

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We studied the kinetics of the reaction of N-acetyl-l-cysteine (NAC or RSH) with cupric ions at an equimolar ratio of the reactants in aqueous acid solution (pH 1.4–2) using UV/Vis absorption and circular dichroism (CD) spectroscopies. Cu2+ showed a strong catalytic effect on the 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) radical (ABTSr) consumption and autoxidation of NAC. Difference spectra revealed the formation of intermediates with absorption maxima at 233 and 302 nm (ε302/Cu > 8 × 103 M−1 cm−1) and two positive Cotton effects centered at 284 and 302 nm. These intermediates accumulate during the first, O2-independent, phase of the NAC autoxidation. The autocatalytic production of another chiral intermediate, characterized by two positive Cotton effects at 280 and 333 nm and an intense negative one at 305 nm, was observed in the second reaction phase. The intermediates are rapidly oxidized by added ABTSr; otherwise, they are stable for hours in the reaction solution, undergoing a slow pH- and O2-dependent photosensitive decay. The kinetic and spectral data are consistent with proposed structures of the intermediates as disulfide-bridged dicopper(I) complexes of types cis-/trans-CuI2(RS)2(RSSR) and CuI2(RSSR)2. The electronic transitions observed in the UV/Vis and CD spectra are tentatively attributed to Cu(I) → disulfide charge transfer with an interaction of the transition dipole moments (exciton coupling). The catalytic activity of the intermediates as potential O2 activators via Cu(II) peroxo-complexes is discussed. A mechanism for autocatalytic oxidation of Cu(I)–thiolates promoted by a growing electronically coupled –[CuI2(RSSR)]n– polymer is suggested. The obtained results are in line with other reported observations regarding copper-catalyzed autoxidation of thiols and provide new insight into these complicated, not yet fully understood systems. The proposed hypotheses point to the importance of the Cu(I)–disulfide interaction, which may have a profound impact on biological systems.

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Section: Discussionmentioning

confidence: 99%

Reaction of N-Acetylcysteine with Cu2+: Appearance of Intermediates with High Free Radical Scavenging Activity: Implications for Anti-/Pro-Oxidant Properties of Thiols

Valent

Bednářová

Schreiber

et al. 2022

IJMS

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“…The coordination geometry around the Cu1 atom is distorted from regular tetrahedral, with bond angles varying from 85.5(1)° (N1–Cu1–S1) to 134.6(1)° (S1–Cu1–S2A), probably due to formation of the pentagonal rings [Cu1–S2A–C–C–S3A] and the steric hindrance between two macrocycles. The pyridine N strongly binds to the metal center [Cu1–N1 2.055(2) Å], and the Cu–S bond distances are typical [2.275(1)–2.359(1) Å] …”

Section: Resultsmentioning

confidence: 99%

Influence of the Reaction Sequence on the Complexation of an NS₄-Macrocycle with Cd^II and Cu^I Salts Leading to the Formation of Supramolecular Isomers and an Endo/Exocyclic Cu^I Complex

Kim

Park

et al. 2021

Inorg. Chem.

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In the construction of metallosupramolecules, the reaction sequence in a three-reactant system (one ligand plus two metal ions) could be one of the controlling factors influencing the outcome of the reaction. In this work, the formation of supramolecular isomers (1 and 2) and an endo/exocyclic Cu+ complex (4) of the NS4-macrocycle (L) via different sequential metal addition protocols (routes I–III) is reported. In one-pot reactions of L with Cu(CH3CN)4PF6 in the absence (route I) and presence (route II) of CdI2, a cyclic dimer CuI complex, [Cu2(L)2](PF6)2 (1), and a one-dimensional coordination polymer, [Cu2(L)2] n ·n[CdI4] (2), were obtained, respectively. Interestingly, the complex cations in 1 and 2 are supramolecular isomers formed via cyclization and polymerization upon complexation, respectively, probably due to different geometric and electronic complementarities, via the C–H···X– hydrogen bonds, between L and the counterion. In the two-step reaction (route III), an endocyclic Cd2+ complex, [Cd(L)I2] (3), obtained in the first step was utilized in the following reaction with Cu(CH3CN)4PF6, giving rise to an endo/exocyclic tetranuclear Cu+ complex, [Cu4(L)2(CH3CN)6](PF6)4 (4), via Cd2+ → 2Cu+ substitution, which is not accessible by conventional procedures. Solution studies by comparative NMR and electrospray ionization mass spectroscopy also support metal substitution by showing the stronger binding affinity of Cu+ over Cd2+. These results demonstrate that the metal substitution protocol could be useful for reaching novel metallosupramolecules difficult to obtain by other methods.

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“…Given the apparent thermodynamic stability of the "Atlas-sphere" structure type, as revealed by the [37][38][52][53][54][55] it is likely that many of these complexes also feature a [Cu12(SR)6] 6+ core. That being said, other core structures are also possible, including [Cu4(SR)4] (R = 2,6-(Me3Si)2C6H3, 2,4,6-i Pr3-C6H2), [56][57] 64,[66][67][68] [Cu5(SR)7] 2-(R = Me, Ph), 62,[69][70] [Cu6(SR)6(µ6-Br)] (R = 1-(thiolato)triptycene), 71 [Cu8(SR)8] (R = 2,4,6-i Pr3-C6H2), 57, 72 [Cu8(SR)6Cl6] 2+ (R = CH2CH2NH3), 55 The reactivity of Cu(I) and Cu(II) salts with thiols and thiolates is actually well explored. 74 Despite this long history, there is no crystallographically authenticated example of this reaction resulting in formation of a Cu(0)-containing product.…”

Section: Clustermentioning

confidence: 99%

“…74 Despite this long history, there is no crystallographically authenticated example of this reaction resulting in formation of a Cu(0)-containing product. 71 It is also useful to survey the reactivity of Ag and Au salts with thiols. For instance, reaction of AgNO3 with RSH/NEt3 in MeCN resulted in formation of [Ag(SR)]n oligomers.…”

Section: Clustermentioning

confidence: 99%

Synthesis and Characterization of “Atlas-Sphere” Copper Nanoclusters: New Insights into the Reaction of Cu²⁺ with Thiols

Cook¹,

Jones²,

Teat

et al. 2019

Inorg. Chem.

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Thiolates are a widely used ligand class for the stabilization of M(0)-containing gold and silver nanoclusters. Curiously, though, very few thiolate-stabilized Cu nanoclusters are known. Herein, we report an examination of the reactivity of RSH (R = CH2CH2Ph, n-Bu, n-C12H25) with Cu 2+ under anhydrous conditions. These reactions result in formation of fluorescent "Atlas-sphere"-type copper-thiolate nanoclusters, including [Cu12(SR´)6Cl12][(Cu(R´SH))6] (2, R´ = n Bu) and [H(THF)2]2[Cu17(SR´´)6Cl13(THF)2(R´´SH)3] (3, R´´ = CH2CH2Ph), which were characterized by X-ray crystallography, ESI-MS, NMR spectroscopy, as well as XANES and EXAFS. Consistent with our X-ray crystallographic results, the edge energies of 2 and 3 suggest they are constructed exclusively with Cu(I) ions. Similarly, EXAFS of 2 and 3 reveal long Cu-Cu pathlengths, which is also consistent with their X-ray crystal structures. Given these results, as well as past work on Cu 2+ /thiol reactivity, we suggest that Cu(0) is unlikely to be formed by reaction of Cu 2+ with a thiol, and that previous reports of Cu(0)-containing nanoclusters synthesized by reaction of Cu 2+ with thiols are likely erroneous.

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Synthesis and Structures of Cuprous Triptycylthiolate Complexes

Cited by 18 publications

References 85 publications

Reaction of N-Acetylcysteine with Cu2+: Appearance of Intermediates with High Free Radical Scavenging Activity: Implications for Anti-/Pro-Oxidant Properties of Thiols

Reaction of N-Acetylcysteine with Cu2+: Appearance of Intermediates with High Free Radical Scavenging Activity: Implications for Anti-/Pro-Oxidant Properties of Thiols

Influence of the Reaction Sequence on the Complexation of an NS₄-Macrocycle with Cd^II and Cu^I Salts Leading to the Formation of Supramolecular Isomers and an Endo/Exocyclic Cu^I Complex

Synthesis and Characterization of “Atlas-Sphere” Copper Nanoclusters: New Insights into the Reaction of Cu²⁺ with Thiols

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Synthesis and Structures of Cuprous Triptycylthiolate Complexes

Cited by 18 publications

References 85 publications

Reaction of N-Acetylcysteine with Cu2+: Appearance of Intermediates with High Free Radical Scavenging Activity: Implications for Anti-/Pro-Oxidant Properties of Thiols

Reaction of N-Acetylcysteine with Cu2+: Appearance of Intermediates with High Free Radical Scavenging Activity: Implications for Anti-/Pro-Oxidant Properties of Thiols

Influence of the Reaction Sequence on the Complexation of an NS4-Macrocycle with CdII and CuI Salts Leading to the Formation of Supramolecular Isomers and an Endo/Exocyclic CuI Complex

Synthesis and Characterization of “Atlas-Sphere” Copper Nanoclusters: New Insights into the Reaction of Cu2+ with Thiols

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Influence of the Reaction Sequence on the Complexation of an NS₄-Macrocycle with Cd^II and Cu^I Salts Leading to the Formation of Supramolecular Isomers and an Endo/Exocyclic Cu^I Complex

Synthesis and Characterization of “Atlas-Sphere” Copper Nanoclusters: New Insights into the Reaction of Cu²⁺ with Thiols