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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Copper(II) complexes of thioether-substituted salcyen and salcyan derivatives and their silver(I) adducts
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Copper(II) complexes of thioether-substituted salcyen and salcyan derivatives and their silver(I) adducts

机译：硫醚取代的水杨和水杨酸衍生物的铜（II）配合物及其银（I）加合物

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New syntheses are reported of 5-tert-butyl-2-hydroxy-3-methylsulfanylbenzaldehyde,5-tert-butyl-2-hydroxy-3-phenylsulfanyl-benzaldehyde,and salcyen (H_2L~1-H_2L~3) and salcyan (H_2L~4-H_2L~6)-type ligands derived from these aldehydes and from 5-tert-butyl-2-hydroxybenzaldehyde.The complexes [CuL] (L~(2-) = [L~1]~(2-)-[L~6]~(2-)) bearing sulfanyl substituents each show two distinct voltammetric ligand-based oxidations under the same conditions,the first of which is chemically reversible.The first oxidation product is much longer lived by coulometry for the salcyen than for the salcyan ligand complexes,despite the latter having a substantially lower oxidation potential.The lifetimes of all the ligand oxidation products in this system are substantially smaller than for similar compounds derived from 3,5-di(tert-butyl)-2-hydroxybenzaldehyde (Dalton Trans.,2004,2662).Attempted chemical oxidation of the Schiff base compounds using AgBF_4 yielded instead stable silver(I) adducts.A crystal structure of one such compound showed that the Ag atom was coordinated in a slightly bent geometry by the two ligand sulfanyl groups,with two additional long-range Ag ...O interactions to the phenoxide donors.EPR spectra showed that some of these silver adducts dimerise in CH_2C1_2,probably through basal,apical intermolecular Cu-O...Cu bridging.In contrast the parent copper(II) complexes are all monomeric in this solvent by EPR.
机译：据报道，合成了5-叔丁基-2-羟基-3-甲基硫烷基苯甲醛，5-叔丁基-2-羟基-3-苯基硫烷基苯甲醛，水杨基（H_2L〜1-H_2L〜3）和水杨基（H_2L）。由这些醛和5-叔丁基-2-羟基苯甲醛衍生的〜4-H_2L〜6）型配体。络合物[CuL]（L〜（2-）= [L〜1]〜（2-）- [L〜6]〜（2-））带有硫烷基取代基，在相同条件下各显示两个不同的基于伏安性配体的氧化，第一个是化学可逆的。对于该四价铬配体配合物，尽管后者的氧化电位要低得多。该体系中所有配体氧化产物的寿命都比由3,5-二（叔丁基）-2-羟基苯甲醛衍生的类似化合物的寿命短（Dalton Trans。，2004,2662）。使用AgBF_4尝试对席夫碱化合物进行化学氧化会生成稳定的银（I）加合物。一种这样的化合物的结构表明，Ag原子由两个配体硫烷基以微弯曲的几何结构进行配位，并且与酚盐供体有两个额外的远程Ag ... O相互作用。EPR谱显示其中一些银加合物CH_2C1_2中的二聚体可能是通过基础的，根尖的分子间Cu-O ... Cu桥连形成的。相反，通过EPR，母体铜（II）配合物在该溶剂中都是单体。

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