基于1-(2-吡啶甲基)-1, 2, 4-三唑的金属有机化合物的合成及反应研究

本文合成了1-（2-吡啶甲基）-1，2，4-三唑（L），并研究了其与有机锡和羰基钼（钨）的配位反应，合成了通过三唑4位氮原子以单齿形式配位的有机锡衍生物L₂SnR₂Cl₂（R=Me，n-Bu或Ph）和羰基金属配合物LM（CO）₅（M=Mo或W），以及N，N螯合双齿配位的四羰基金属配合物LM（CO）₄。当用氯化苄处理L时，制得了相应的三唑盐，该盐用氧化银处理后与M（CO）₅THF或M（CO）₄（NHC₅H₁₀）₂（NHC₅H₁₀为哌啶）反应，得到了基于三唑的氮杂环卡宾衍生物L’M（CO）₅和L’M（CO）₄（L’=1-（2-吡啶甲基）-4-苄基-1，2，4-三唑-5-碳烯）。X-射线单晶衍射分析表明，在L’M（CO）₅中氮杂环卡宾配体L’表现为通过卡宾碳配位的单齿配体；而在L’M（CO）₄中，L’表现为通过卡宾碳和吡啶氮原子配位的螯合C，N]双齿配体。

Synthesis and Related Reactivity of Organometallic Complexes Based on 1-(2-Pyridylmethyl)-1,2,4-triazole

1-(2-Pyridylmethyl)-1,2,4-triazole (L) has been synthesized by the reaction of 1,2,4-triazole with 2-chloromethylpyridine. Reaction of Lwith R₂SnCl₂ gave 2:1 adducts of L₂SnR₂Cl₂ (R=Me, n-Bu or Ph). Treatment of Lwith M(CO)₆ yielded complexes LM(CO)₅ and LM(CO)₄ (M=Mo or W). X-ray structural analyses indicated that Lacted as a monodentate ligand through the exodentate nitrogen atom of the triazole ring in complexes L₂SnR₂Cl₂ and LM(CO)₅, while a N,N-chelating bidentate ligand was observed in LM(CO)₄. 1-(2-Pyridylmethyl)-4-benzyl-1,2,4-triazolium chloride was obtained by the reaction of Lwith PhCH₂Cl. Treatment of this triazolium salt with Ag₂O, and succedent metal transfer reaction with M(CO)₅THFor M(CO)₄(NHC₅H₁₀)₂ (NHC₅H₁₀ represents piperidine) yielded N-heterocyclic carbene complexes L'M(CO)₅ and L'M(CO)₄ (L'=1-(2-pyridylmethyl)-4-benzyl-1,2,4-triazol-5-ylidene), respectively. In the former, L' acted as a monodentate ligand by the carbene carbon, while L' served as a chelating bidentate ligand by the pyridyl nitrogen and the carbene carbon atoms in the latter.