| Autor: |
Dodonov VA; G. A. Razuvaev Institute of Organometallic Chemistry , Russian Academy of Sciences , Tropinina 49 , Nizhny Novgorod 603950 , Russian Federation.; Institute of Inorganic Chemistry , Karlsruhe Institute of Technology , Engesserstraße 15 , Karlsruhe 76131 , Germany., Morozov AG; G. A. Razuvaev Institute of Organometallic Chemistry , Russian Academy of Sciences , Tropinina 49 , Nizhny Novgorod 603950 , Russian Federation., Rumyantsev RV; G. A. Razuvaev Institute of Organometallic Chemistry , Russian Academy of Sciences , Tropinina 49 , Nizhny Novgorod 603950 , Russian Federation., Fukin GK; G. A. Razuvaev Institute of Organometallic Chemistry , Russian Academy of Sciences , Tropinina 49 , Nizhny Novgorod 603950 , Russian Federation., Skatova AA; G. A. Razuvaev Institute of Organometallic Chemistry , Russian Academy of Sciences , Tropinina 49 , Nizhny Novgorod 603950 , Russian Federation., Roesky PW; Institute of Inorganic Chemistry , Karlsruhe Institute of Technology , Engesserstraße 15 , Karlsruhe 76131 , Germany., Fedushkin IL; G. A. Razuvaev Institute of Organometallic Chemistry , Russian Academy of Sciences , Tropinina 49 , Nizhny Novgorod 603950 , Russian Federation.; College of Chemistry and Materials Science , Northwest University , Xi'an 710069 , China. |
| Abstrakt: |
The synthesis of electron-deficient gallium- and aluminum-centered species containing a redox-active dpp-Bian ligand (dpp-Bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) is described. The reaction of digallane [(dpp-Bian)Ga-Ga(dpp-Bian)] with [Ph 3 C][PF 6 ] or AgPF 6 resulted in polyoxidized species [(dpp-Bian)GaF 2 ] 2 ( 1 ), [(dpp-Bian)H 2 ][PF 6 ] ( 2 ), and [(dpp-Bian)GaF(O 2 PF 2 )] 2 ( 3 ). The reaction of digallane with B(C 6 F 5 ) 3 led to electron-deficient gallylene [(dpp-Bian)GaB(C 6 F 5 ) 3 ] 4 of a dpp-Bian radical anion. The soft oxidation of digallane with tosyl cyanide gave the trinuclear cationic species [(dpp-Bian)Ga(Tos) 3 Ga(Tos) 3 Ga(dpp-Bian)][Ga(CN) 4 ] ( 5 ) containing dpp-Bian radical anions. The reaction of [(dpp-Bian)AlEt 2 ] with 1 equiv of [Ph 3 C][B(C 6 F 5 ) 4 ] resulted in the cationic complex [(dpp-Bian)AlEt 2 ][B(C 6 F 5 ) 4 ] ( 6 ) of neutral dpp-Bian, while the treatment of [(dpp-Bian)AlEt(Et 2 O)] with 1 equiv of [Ph 3 C][B(C 6 F 5 ) 4 ] resulted in the compound [(dpp-Bian)AlEt(Et 2 O)][B(C 6 F 5 ) 4 ] ( 7 ) of a dpp-Bian radical anion. The reaction of diethylaluminum derivative [(dpp-Bian)AlEt 2 ] with 1 equiv of B(C 6 F 5 ) 3 gave the cationic complex [{(dpp-Bian)AlEt} 2 F][EtB(C 6 F 5 ) 3 ] ( 8 ) containing radical-anion dpp-Bian ligands. The paramagnetic compounds 1 , 2 , 4 , 5 , 7 , and 8 were characterized by electron paramagnetic resonance spectroscopy, and the diamagnetic complex 6 was characterized by NMR spectroscopy. The molecular structures of 1 - 6 and 8 were established by single-crystal X-ray diffraction analysis. Compounds 4 and 6 - 8 were found to be active initiators for immortal ring-opening polymerization of ε-caprolactone. |
