Coordination and Oxidation of N,N'-Bis(o-mercaptophenyl)ethylenediamine (HSNNSH) by VO2+: {V(-SNNS-)}4(.mu.-O)4 and Tetrabenzotetrathiatetraazacycloeicosane

Tsagkalidis, Wenerios; Rodewald, Dieter; Rehder, Dieter

doi:10.1021/ic00111a047

Cited by 29 publications

(17 citation statements)

References 1 publication

(1 reference statement)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…On the other hand, thiolates can be oxidized to disulfides in the presence of VO 2+ ,36–38 a reaction that can be accompanied by an abstraction of the oxo group37, 38 and concomitant formation of non‐oxo V IV complexes 38. The VO 2+ ‐mediated oxidation of thiolate has also been observed for the reaction between the dithiolate 6 a and [VO(acac) 2 ] (acac=acetylacetonate(1−)), which leads to the cyclic bis(disulfide) 6 b (see Scheme a).…”

Section: Resultsmentioning

confidence: 99%

Formation, Preservation, and Cleavage of the Disulfide Bond by Vanadium

Wang

Behrens

Farahbakhsh

et al. 2003

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Reaction of the disulfide [HpicanS](2) (HpicanS is the carboxamide based on picolinate (pic) and o-mercaptoaniline (anS); the [] brackets are used to denote disulfides) with [VOCl(2)(thf)(2)] leads to reductive scission of the disulfide bond and formation of the mixed-valence (V(IV)/V(V)) complex anion [(OVpicanS)(2)mu-O](-) (1), with the dianionic ligand coordinating through the pyridine-N atom, the deprotonated amide-N atom, and thiophenolate-S atom. Reductive cleavage of the SbondS bond is also observed as [VCl(2)(tmeda)(2)] (tmeda=tetramethylethylenediamine) is treated with the disulfides [HsalanS](2) or [HvananS](2) (HsalanS and HvananS are the Schiff bases formed between o-mercaptoaniline and salicylaldehyde (Hsal) or vanillin (Hvan), respectively), yielding the V(III) complexes [VCl(tmeda)(salanS)] (2 a), or [VCl(tmeda)(vananS)] (2 b). The disulfide bond remains intact in the aerial reaction between [HsalanS](2) and [VCl(3)(thf)(3)] to yield the V(V) complex [VOCl[salanS](2)] (3), where (salanS)(2-) coordinates through the two phenolate and one of the imine functions. The S-S bond is also preserved as [VO(van)(2)] or [VO(nap)(2)] (Hnap=2-hydroxynaphthalene-1-carbaldehyde) is treated with bis(2-aminophenyl)disulfide, [anS](2), a reaction which is accompanied by condensation of the aldehyde and the diamine, and complexation of the resulting bis(Schiff bases) [HvananS](2) or [HnapanS](2) to form the complexes [VO[vananS](2)] (4 a) or [VO[napanS](2)] (4 b). In 4 a and 4 b, the phenolate and imine functions, and presumably also one of the disulfide-S atoms, coordinate to V(IV). 2-Mercaptophenyl-2'-pyridinecarboxamide (H(2)picanS) retains its identity in the presence of V(III); reaction between [VCl(3)(thf)(3)] and H(2)picanS yields [V[picanS](2)](-) (5). The dithiophenolate 2,6-bis(mercaptophenylthio)dimethylpyridine (6 a) is oxidized, mediated by VO(2+), to the bis(disulfide) octathiadiaza-cyclo-hexaeicosane 6 b. The relevance of these reactions for the speciation of vanadium under physiological conditions is addressed. [HNEt(3)]-1.0.5 NEt(3,) 3.3 CH(2)Cl(2), [HsalanS](2), [HNEt(3)]-5, and 6 b.4 THF have been characterized by X-ray diffraction analysis.

show abstract

Section: Resultsmentioning

confidence: 99%

Formation, Preservation, and Cleavage of the Disulfide Bond by Vanadium

Wang

Behrens

Farahbakhsh

et al. 2003

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

“…Complexes with a variety of bi-and tetradentate S-donor functionalities have been prepared as model complexes for Nase. [657][658][659][660] These complexes have some structural similarities to the binding site of Nase. However, in contrast to the isolated cofactor, they fail to convert N 2 to NH 3 .…”

Section: Structural Model Complexes Of the Vfe Cofactor Binding Sitementioning

confidence: 99%

The Chemistry and Biochemistry of Vanadium and the Biological Activities Exerted by Vanadium Compounds

et al. 2004

View full text Add to dashboard Cite

“…[1,18] The structure of [{VOCl 2 (MeSCH 2 CH 2 SMe)} 4 ] is quite different (Table 3, Figure 2) and has a tetranuclear V 4 O 4 core. The structure can either be described as based upon square pyramidal [19] The closest analogue to the structure of [{VOCl 2 [7,22,23] The solid [VCl 4 (dithioether)] are extremely moisture-sensitive, evolving yellow fumes in air and turning green-blue. However, in contrast to the V V [VOCl 3 (dithioether)] complexes, they are stable in the dry box for several weeks.…”

Section: Introductionmentioning

confidence: 99%