The reaction of fac-[ReX(CH₃CN)₂(CO)₃] (X = Cl, Br) with N-phenyl-[4-(dimethylamino)benzaldehyde] thiosemicarbazone (HL^A) or N-4-methoxybenzyl-[4-(dimethylamino)benzaldehyde] thiosemicarbazone (HL^B) under controlled synthetic conditions gave 4 mononuclear [ReX(HL)(CO)₃] (X = Cl, Br) and 16 dinuclear [Re₂L₂(CO)₆] compounds. These complexes were obtained as single crystals, and their structures were established by X-ray diffraction. The structural study of these dimers showed the formation of several solvates, the presence of linkage isomerism, and the stabilization of four- and/or five-membered chelate rings. The different ligand coordination modes (a new μ-κ²-S,N2:κ-N3 coordination mode for a thiosemicarbazone ligand was observed), the conformation of the thiosemicarbazone chain in each case, the formal symmetry of the dimers, and the role of the synthetic procedure in the stability of the different chelate rings were analyzed and are discussed. Theoretical calculations in the gas phase were performed for the dimers with the HL^A ligand in order to identify the thermodynamically most stable species. The behavior and structural stability of dimers in dimethyl sulfoxide and acetone solutions was investigated by ¹H NMR spectroscopy. The strength of the Re^I–L bond in solution was evidenced by the formation of [Re₂(L^NO₂)₂(CO)₆] and [Re(L^A)(py)(CO)₃] upon reaction of the corresponding dimer with concentrated nitric acid and pyridine, respectively.

中文翻译：

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Novel（I）的新型双核N-取代的4-（二甲基氨基）苯甲醛硫代氨基甲酸氨基甲酸酯的合成：四元和/或五元螯合环的形成，构象分析和反应性。

的反应FAC - [REX（CH ₃ CN）₂（CO）₃ ]（X =氯，溴）与Ñ苯基[4-（二甲基氨基）苯甲醛]缩氨基硫脲（HL^甲）或ñ -4-甲氧基苄基[4-（二甲基氨基）苯甲醛]硫半卡巴zone （HL ^B）在控制的合成条件下得到4个单核[ReX（HL）（CO）₃ ]（X = Cl，Br）和16个双核[Re ₂ L ₂（CO）₆]化合物。这些配合物以单晶形式获得，其结构通过X射线衍射确定。这些二聚体的结构研究表明，形成了几种溶剂化物，存在连接异构现象，并稳定了四元和/或五元螯合环。不同的配位体的配位模式（一个新的μ-κ ² -S，N 2：观察到了缩氨基硫脲配位体κ-N3协调模式），在每种情况下，二聚体的正式对称的缩氨基硫脲链的构象，和角色分析并讨论了合成方法对不同螯合环稳定性的影响。使用HL ^A对二聚体进行气相理论计算为了鉴定热力学上最稳定的物种。通过¹ H NMR光谱研究了二聚体在二甲基亚砜和丙酮溶液中的行为和结构稳定性。溶液中Re ^I –L键的强度由[Re ₂（L ^{NO ₂}）₂（CO）₆ ]和[Re（L ^A）（py）（CO）₃ ]的形成证明。分别与浓硝酸和吡啶形成二聚体。