The ligand tris(6-tert-butyl-3-thiopyridazinyl)methane ([Tntm]H) was synthesized by the reaction of 6-tert-butyl-3-thiopyridazine with bromoform and reacted with zinc bis(trimethylsilylamide) (Zn(N{SiMe₃}₂)₂) to form [Tntm]Zn(N{SiMe₃}₂) (1). This complex further reacts with protic and acidic substrates, generating the zinc thiolate complex [Tntm]Zn(StBu) (2) and zinc benzoate complex [Tntm]Zn(O₂C-Me₂C₆H₃) (3a). In all compounds [Tntm] was found to have tridentate coordination to the metal center in a κ³-C,N,N fashion, as established by single-crystal X-ray diffraction analyses. In solution, rapid dynamic κ³/κ⁴ equilibrium occurs at room temperature, while ¹H NMR spectroscopy at −30 °C confirms the asymmetric solid-state structure. Furthermore, complex 3a shows a rearrangement reaction in solution where the ligand isomerizes to give a κ⁴-C,N,N,S (3b) and a κ⁴-C,N,S,S isomer (3c), respectively. Density functional theory (DFT) calculations reveal 3b and 3c to be 13.7 and 15.6 kJ/mol more stable in methylene chloride than 3a, respectively. All compounds were fully characterized via ¹H, ¹³C, and variable temperature NMR spectroscopy, as well as elemental and single-crystal X-ray diffraction analysis.

中文翻译：

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硫代哒嗪基甲烷基蝎形配体的合成与表征：锌配合物的形成和重排反应

配体三（6-叔丁基-3- thiopyridazinyl）甲烷（[Tntm 1 H）通过6-反应合成叔丁基-3- thiopyridazine与溴仿，用锌双（三甲基硅烷基）（锌（N反应{SiMe ₃ } ₂）₂）形成[Tntm] Zn（N {SiMe ₃ } ₂）（1）。该配合物进一步与质子和酸性底物反应，生成硫醇锌配合物[Tntm] Zn（S t Bu）（2）和苯甲酸锌配合物[Tntm] Zn（O ₂ C-Me ₂ C ₆ H ₃）（3a））。在所有化合物[Tntm]被发现具有在κ与金属中心配位的三齿³ - C，N，N的方式，通过单晶X射线衍射分析所确立。在溶液中，快速动态κ ³ /κ ⁴平衡在室温下发生，而^1个在-30 H NMR光谱℃下确认了非对称的固态结构。此外，复杂的图3a示出了在溶液中的重排反应，其中所述配体异构化为得到κ ⁴ - C，N，N，S（图3B）和κ ⁴ - C，N，S，S异构体（3C）， 分别。密度泛函理论（DFT）计算显示3b和3c在二氯甲烷中的稳定性分别比3a稳定13.7和15.6 kJ / mol 。所有化合物均通过¹ H，¹³ C和可变温度NMR光谱以及元素和单晶X射线衍射分析进行了全面表征。