Amino Group Functionalized N‑Heterocyclic 1,2,4-Triazole-Derived Carbenes: Structural Diversity of Rhodium(I) Complexes
Abstract
The synthesis of the amino group functionalized NHC precursor 1-<i>tert</i>-butyl-4-(2-((dimethylamino)methyl)-phenyl)-3-phenyl-4<i>H</i>-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[Rh(COD)Cl]<sub>2</sub>, [Rh(cyclooctene)<sub>2</sub>Cl]<sub>2</sub>, and [Rh(ethylene)<sub>2</sub>Cl]<sub>2</sub>, 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)]<sup>+</sup>[BF<sub>4</sub>]<sup>−</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 analysisSimilar works
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