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(英文)

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 L with R₂SnCl₂ gave 2:1 adducts of L₂SnR₂Cl₂ (R=Me, n-Bu or Ph). Treatment of L with M(CO)₆ yielded complexes LM(CO)₅ and LM(CO)₄ (M=Mo or W). X-ray structural analyses indicated that L acted 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 L with PhCH₂Cl. Treatment of this triazolium salt with Ag₂O, and succedent metal transfer reaction with M(CO)₅THF or 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. CCDC: 973255, 1; 973463, 5; 973464, 8; 973465, 10.