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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Asymmetric sulfur atom coordination in a copper(II)dipicolylamine(DPA)complex with a thioglycoside ligand
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Asymmetric sulfur atom coordination in a copper(II)dipicolylamine(DPA)complex with a thioglycoside ligand

机译：具有硫糖苷配体的铜（II）二甲基吡啶胺（DPA）配合物中的不对称硫原子配位

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摘要

The 2,2'-dipicolylamine(DPA)-tethered thioglycoside ligand,N,N-bis(2-pyridylmethyl)-2-aminoethyl 1-deoxy-1-thio-2,3,4,6-tetra-O-acetyl-beta-D-glucopyranoside(sL1),has been prepared and its copper(II)complex synthesized.Using copper(II)chloride,the copper complex was isolated as a chloride-bound species formulated as [Cu(sL1)Cl(ClO4)](1).The corresponding O-glycoside complex([Cu(L1)Cl](ClO4),2)was also prepared using L1(N,N-bis(2-pyridylmethyl)-2-aminoethyl 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranoside),and both complexes were characterized and compared by means of X-ray crystallography,cyclic voltammetry,electronic absorption and circular dichroism(CD)spectra.Although both complexes exhibited similar copper coordination geometries,the absolute configuration of the O/S chiral center generated by the copper coordination was inverted.The electronic and CD spectra of acetonitrile solutions of 1 and 2 were different likely due to the presence of a copper-sulfur charge-transfer band for 1.Complex 1 also exhibits a large Cotton effect around 700 nm.The corresponding d-d transition of the copper(II)center reveals that the asymmetric copper-sulfur(oxygen)coordination remains even in solution.
机译：2,2'-二吡啶甲胺（DPA）系的硫代糖苷配体N，N-双（2-吡啶基甲基）-2-氨基乙基1-脱氧-1-硫代2,3,4,6-四-O-乙酰基制备了β-D-吡喃葡萄糖苷（sL1），合成了其铜（II）配合物。使用氯化铜（II），将铜配合物分离为氯化物结合的物质，配制成[Cu（sL1）Cl（ClO4） ）]（1）。还使用L1（N，N-双（2-吡啶基甲基）-2-氨基乙基2,3， 4,6-四-O-乙酰基-β-D-吡喃葡萄糖苷），并通过X射线晶体学，循环伏安法，电子吸收和圆二色性（CD）光谱对两种配合物进行了表征和比较。铜配位的几何结构，由铜配位产生的O / S手性中心的绝对构型被颠倒.1和2的乙腈溶液的电子和CD光谱可能不同，因为存在铜-硫电荷转移带对于1.Co复合体1在700 nm附近也表现出较大的Cotton效应。铜（II）中心的相应d-d跃迁表明，即使在溶液中，铜-硫（氧）配位的不对称配位也仍然存在。

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