A Halide‐Induced Copper(I) Disulfide/Copper(II) Thiolate Interconversion

Neuba, Adam; Haase, Roxana; Meyer‐Klaucke, Wolfram; Flörke, Ülrich; Henkel, Gerald

doi:10.1002/anie.201102714

Cited by 58 publications

(66 citation statements)

References 49 publications

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“…This conversion, in which Cu II is reduced to Cu I and the thiolate ligands are oxidized to form a disulfide bond, takes place intramolecularly and in some cases can be reversed in a controlled manner [11][12][13]. It has been reported that small ligand changes can determine the formation of either a Cu II l-thiolate or a Cu I disulfide complex [14].…”

Section: Introductionmentioning

confidence: 98%

Coordination of new disulfide ligands to CuI and CuII: Does a CuII μ-thiolate complex form?

Ording-Wenker

Siegler

Bouwman

2015

Inorganica Chimica Acta

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Section: Introductionmentioning

confidence: 98%

Coordination of new disulfide ligands to CuI and CuII: Does a CuII μ-thiolate complex form?

Ording-Wenker

Siegler

Bouwman

2015

Inorganica Chimica Acta

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“…23 and 2 Cl 2 ] are synthetically connected by a chloride-induced disulphidethiolate interconversion. Disulphide cleavage and addition of chloride anions lead to significant structural changes; the six-membered Cu 2 S 4 -ring is transformed into a bis(μ-S) dicopper unit [86]. Table 14 illustrates the general tendency: upon oxidation of the coordinated copper ion, the C¼N bond stretches and the ρ-value increases.…”

Section: Guanidine-thio Ligandsmentioning

confidence: 98%

Guanidine Metal Complexes for Bioinorganic Chemistry and Polymerisation Catalysis

Stanek

Rösener

Metz

et al. 2015

Topics in Heterocyclic Chemistry

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Guanidines are highly useful ligands which have conquered coordination chemistry within the last 20 years. Their CN 3 moiety allows multiple substitution patterns which enables tailoring them to a large variety of applications, ranging from bioinorganic coordination chemistry via medicinal chemistry to polymerisation catalysis. In bioinorganic chemistry, guanidines gave important stimuli in the modelling of copper type 1, 2 and 3 enzymes. This review provides with a comprehensive overview on complexes which have been reported with neutral guanidine ligands. Peralkylated guanidines as well as bicyclic or more complex guanidine-comprising entities are described in their coordination chemistry with transition and main-group metals. The structural features of the complexes as well as their most prominent features in bioinorganic chemistry or polymerisation catalysis are highlighted. Hereby, the role of the delocalisation of the positive charge within the guanidine unit gained during coordination is discussed in its importance for efficient and robust coordination. The delocalisation within the CN 3 unit can be measured by the structural value ρ which is discussed for numerous systems. The charge delocalisation makes neutral guanidines versatile and efficient for the stabilisation of highly different coordination modes and a large variety of oxidation states.

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“…Addition of a methyl group next to the sulfur in the disulfide bond, however, results in significantly higher activity (entries [3][4][5][6]. Changing the bridge between the tertiary amine and the pyridyl groups from a methylene to an ethylene spacer at two positions leads to an increase in activity (entry 3 vs. 8), but at four positions it leads to a dramatic decrease in activity (entry 3 vs. 9).…”

Section: Dalton Transactions Papermentioning

confidence: 99%

“…[1][2][3][4][5][6] It has been reported that small changes in the ligand structure can direct the reaction with copper salts towards the formation of either a Cu II µ-thiolate or a Cu I disulfide complex and that these species can interconvert (Fig. 1a).…”

Section: Introductionmentioning

confidence: 99%

Catalytic catechol oxidation by copper complexes: development of a structure–activity relationship

et al. 2015

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A large library of Cu II complexes with mononucleating and dinucleating ligands was synthesized to investigate their potential as catalysts for the catalytic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC). X-ray structure determination for a number of these complexes revealed relatively large Cu⋯Cu distances and the formation of polymeric species. Comparison of the 3,5-DTBC oxidation rates showed that ligands that stabilize the biomimetic dinuclear Cu II µ-thiolate complex also result in copper compounds that are much more active in the oxidation of 3,5-DTBC. This oxidation activity is however inhibited by the presence of chloride ions. The highest k cat that was observed was 6900 h, which is one of the highest turnover frequencies reported so far for catechol oxidation in CH 3 CN.

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A Halide‐Induced Copper(I) Disulfide/Copper(II) Thiolate Interconversion

Cited by 58 publications

References 49 publications

Coordination of new disulfide ligands to CuI and CuII: Does a CuII μ-thiolate complex form?

Coordination of new disulfide ligands to CuI and CuII: Does a CuII μ-thiolate complex form?

Guanidine Metal Complexes for Bioinorganic Chemistry and Polymerisation Catalysis

Catalytic catechol oxidation by copper complexes: development of a structure–activity relationship

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