Amino Group Functionalized N-Heterocyclic 1,2,4-Triazole-Derived Carbenes: Structural Diversity of Rhodium(I) Complexes

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• 作者：Jan Turek ; Illia Panov ; Michal Hor谩膷ek ; Zden臎k 膶erno拧ek ; Zde艌ka Pad臎lkov谩 ; Ale拧 R暖啪i膷ka
• 刊名：Organometallics
• 出版年：2013
• 出版时间：December 9, 2013
• 年：2013
• 卷：32
• 期：23
• 页码：7234-7240
• 全文大小：308K
• 年卷期：v.32,no.23(December 9, 2013)
• ISSN：1520-6041

文摘

The synthesis of the amino group functionalized NHC precursor 1-<i>terti>-butyl-4-(2-((dimethylamino)methyl)-phenyl)-3-phenyl-4<i>Hi>-1,2,4-triazol-1-ium perchlorate has been developed. The generation and bonding properties of the NHC ligand have been evaluated in reactions toward three Rh(I) complexes鈥擺Rh(COD)Cl]₂, [Rh(cyclooctene)₂Cl]₂, and [Rh(ethylene)₂Cl]₂, respectively. For the first complex, [(NHC)RhCl(COD)], the coordination of the dangling amino group was not observed because of the fully occupied coordination neighborhood of the Rh atom. On the other hand, in the case of [(NHC)RhCl(ethylene)], [(NHC)RhCl(cyclooctene)], [(NHC)Rh(COD)]⁺[BF₄]^{鈭?/sup>, and [(NHC)RhCl(CO)] a strong intramolecular coordination of the amino nitrogen atom was revealed, thus forming the unusual seven-membered diazametallacycle. All of the products of these reactions were characterized in solution by NMR spectroscopy as well as in the solid state by X-ray diffraction analysis.}