| Autor: |
Xue M; College of Chemistry and Chemical Engineering , Central South University , Changsha , Hunan 410083 , P. R. China., Zhuang DL; State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, and Department of Chemistry, College of Chemistry and Chemical Engineering , Xiamen University , Xiamen , Fujian 361005 , P. R. China., Li H; College of Chemistry and Chemical Engineering , Central South University , Changsha , Hunan 410083 , P. R. China., He P; College of Chemistry and Chemical Engineering , Central South University , Changsha , Hunan 410083 , P. R. China., Liu C; College of Chemistry and Chemical Engineering , Central South University , Changsha , Hunan 410083 , P. R. China., Zhu J; State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, and Department of Chemistry, College of Chemistry and Chemical Engineering , Xiamen University , Xiamen , Fujian 361005 , P. R. China., Yi XY; College of Chemistry and Chemical Engineering , Central South University , Changsha , Hunan 410083 , P. R. China. |
| Abstrakt: |
Treatment of [Ir(PPh 3 ) 3 Cl] with 2-[5-(pyridin-2-yl)-1 H -pyrrol-2-yl]pyridine (Hdpp) in refluxing toluene affords an unexpected pyrrole-metalated iridium(III) hydride complex, [Ir(K 2 C,N -dpp)(H)(Cl)(PPh 3 ) 2 ] ( 1 ), via C pyrrole -H activation, while the presence of the base KO t Bu as the deprotonation reagent produces a pyridine-metalated iridium(III) hydride complex, [Ir(K 3 C,N,N -dpp)(H)(PPh 3 ) 2 ] ( 2 ), via C pyridine -H activation. Treatment of [Ir(PPh 3 ) 3 Cl] prepared by a convenient method with Hdpp in the presence of KO t Bu under the refluxing mixture solvent toluene/methanol (2:1, v/v) generates the N,N-chelating complex [Ir(K 2 N,N -dpp)(H)(Cl)(PPh 3 ) 2 ] ( 3 ) together with 1 and the N,N-chelating dihydride complex [Ir(K 2 N,N -dpp)(H) 2 (PPh 3 ) 2 ] ( 4 ). Complex 4 is also readily produced by the reaction of [Ir(PPh 3 ) 3 Cl] and Hdpp in the presence of KO t Bu under refluxing methanol or by the reaction of IrCl 3 and PPh 3 in refluxing 2-ethoxyethanol. Complexes 1 - 4 are fully characterized by NMR, IR, and UV-vis spectroscopy and X-ray diffraction analysis. The dpp - /dpp 2- ligand shows rich coordination capability, of which pyridine- and pyrrole-cyclometalated coordination modes are first reported. The formation of structural isomers 1 and 3 involved the selective activation of the C-H and N-H bonds of Hdpp is rationalized by theoretical calculations. |
