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首页> 外文期刊>Chemistry: A European journal >Formation, Preservation, and Cleavage of the Disulfide Bond by Vanadium
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Formation, Preservation, and Cleavage of the Disulfide Bond by Vanadium

机译：钒对二硫键的形成，保存和裂解

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摘要

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 [(OV-picanS)_2mu-O]~- (1), with the dianionic ligand coordinating through the pyridine-N atom, the deprotonated amide-N atom, and thiophenolate-S atoms. Reductive cleavage of the S-S bond is also observed as [VCl_2(tmeda)_2] (tmeda=tetramethylethylenediamine) is treated with the disulfides {HsalanS}_2 or {Hvan-anS}_2 (HsalanS and HvananS are the Schiff bases formed between o-mercaptoaniline and salicylaldehyde (Hsal) toaniline and salicylaldehyde (Hsal) or vanillin (Hvan), respectively), yielding the V~III complexes [VCl(tmeda)-(salanS)] (2a), or [VCl(tmeda)-(vananS)] (2b). 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, {afS}_2, 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] (4a) or [VO{napanS}_2] (4b). In a and 4b, the phenolate and imine functions, and presumably also one of the disulfide-S atoms, coordinate to V~IV. 2-Mercaptophenyl-2'-pyridinecarboxamide (H_2picanS) retains its identity in the presence of V~III; reactin between [VCl_3(thf)_3] and H_2picanS yields [V-{picanS}_2]~- (5). The dithiophenolate 2,6-bis(mercaptophenylthio)dimethylpyridine (6a) is oxidized, mediated by VO~(2+), to the bis(disulfide) octathiadi-aza-cyclo-hexaeicosane 6b. The relevance of these reactions for the speciation of vanadium under physiological conditions is addressed. [HNEt_3]-1 centre dot 0.5 NEt_3. 3 centre dot 3CH_3Cl_2, {HsalanS}_2, [HNEt_3]-5, and 6b centre dot 4THF have been characterized by X-ray diffraction analysis.
机译：二硫化物{HpicanS} _2（HpicanS是基于吡啶甲酸（pic）和邻巯基苯胺（anS）的羧酰胺; {}括号表示二硫化物）与[VOCl_2（thf）_2]的反应导致还原性断裂二硫键和混合价（V〜IV / V〜V）配位阴离子[（OV-picanS）_2mu-O]〜-（1）的形成，双阴离子配体通过吡啶-N原子配位，去质子化的酰胺-N原子和硫酚盐-S原子。当[VCl_2（tmeda）_2]（tmeda =四甲基乙二胺）用二硫化物{HsalanS} _2或{Hvan-anS} _2处理时（HsalanS和HvananS是在o-巯基苯胺和水杨醛（Hsal）到苯胺和水杨醛（Hsal）或香兰素（Hvan）），生成V〜III配合物[VCl（tmeda）-（salanS）]（2a）或[VCl（tmeda）-（vananS） ）]（2b）。在{HsalanS} _2和[VCl_3（thf）_3]之间的空中反应中，二硫键保持完整，以产生V〜V络合物[VOCl {salanS} _2]（3），其中（salanS）〜（2-）坐标通过两种酚盐和亚胺的功能之一。当[VO（van）_2]或[VO-（nap）_2]（Hnap = 2-羟基萘-1-甲醛）用双（2-氨基苯基）二硫化物{afS} _2处理时，SS键也得以保留反应伴随醛和二胺的缩合，以及生成的双（席夫碱）{HvananS} _2或（HnapanS} _2的络合以形成络合物[VO {vananS} _2]（4a）或[VO { napanS} _2]（4b）。在a和4b中，酚盐和亚胺官能团，并且可能也是二硫键-S原子之一，与V〜IV配位; 2-巯基苯基-2'-吡啶甲酰胺（H_2picanS）保持其身份在V〜III存在下，[VCl_3（thf）_3]与H_2picanS之间的反应生成[V- {picanS} _2]〜-（5）。二硫酚盐2,6-双（巯基苯硫基）二甲基吡啶（6a）被氧化VO〜（2+）介导的双（二硫）八硫二氮杂-环己二十烷烷6b。讨论了这些反应与生理条件下钒的形态形成的相关性[HNEt_3] -1中心点0.5 NEt_3 。3中心点3CH_3C通过X射线衍射分析表征了l_2，{HsalanS} _2，[HNEt_3] -5和6b中心点4THF。

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