The synthesis, structural characterization, and electrochemical properties of N3S2-ligated metal complexes of the ligand 4,10-dithia-1,7,13-triazabicyclo[11.3.3]nonadecane are described. Complexes of NiII, CoII, and RhIII have been characterized by X-ray crystallography as six-coordinate complexes of the pentadentate ligand with Cl- anions occupying the position trans to the secondary amine donor. In addition, the chelation of the N3S2 donor ligand to the reactor-produced radionuclide 105Rh was shown to give a single product in high yield (>98% at pH 5). The ligand is prepared by the template reaction of (N,N‘-bis(2-mercaptoethyl)-1,5-diazacyclooctane)nickel(II), Ni-1, with bis(2-chloroethyl)amine, yielding (S,S‘-(3-aza-1,5-pentanediyl)-N,N‘-bis(2-mercaptoethyl)-1,5-diazacyclooctane-N,N‘,N‘‘,S,S‘)nickel(II) chloride, [Ni(amine)Cl]Cl. Removal of nickel from [Ni(amine)Cl]Cl and subsequent reaction of the ligand with CoCl2 or RhCl3·xH2O afforded (S,S‘-(3-aza-1,5-pentanediyl)-N,N‘-bis(2-mercaptoethyl)-1,5-dia...

中文翻译：

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一种新的大环 N3S2 配体及其镍 (II)、钴 (II)、铑 (III)-103 和铑 (III)-105 配合物

描述了配体 4,10-dithia-1,7,13-triazabicyclo[11.3.3]nonadecane 的 N3S2 连接金属配合物的合成、结构表征和电化学性质。NiII、CoII 和 RhIII 的配合物已通过 X 射线晶体学表征为五齿配体的六配位配合物，其中 Cl-阴离子占据与仲胺供体反式的位置。此外，N3S2 供体配体与反应器产生的放射性核素 105Rh 的螯合显示出高产率的单一产物（>98%，pH 5）。配体是通过（N,N'-双（2-巯基乙基）-1,5-二氮杂环辛烷）镍（II）、Ni-1与双（2-氯乙基）胺的模板反应制备的，得到（S， S'-(3-aza-1,5-pentanediyl)-N,N'-双(2-巯基乙基)-1,5-二氮杂环辛烷-N,N',N'',S,S')镍(II ) 氯化物，[Ni(胺)Cl]Cl。