| 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 |
| Synthesis and Related Reactivity of Organometallic Complexes Based on 1-(2-Pyridylmethyl)-1, 2, 4-triazole |
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| 摘要: 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。 |
| 关键词: 氮配体 卡宾 三唑 钼 钨 锡 |
| 基金项目: 国家自然科学基金（No.20972075）资助项目。 |
| Abstract: 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. |
| Keywords: N ligand carbene triazole molybdenum tungsten tin |
| 投稿时间：2013-12-02 修订日期：2014-01-10 |
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| 陈丹峰,潘爱清,陆继廷,唐良富.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[J].无机化学学报,2014,30(7):1685-1693. |
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