A new type of dianionic Ir(Ⅲ) CCC pincer complexes(SNHC-Ir, 1a–1c) is successfully designed and synthesized by developing a one-step methodology, which involves an initial coordination of Ir(I) with the NHC and subs...A new type of dianionic Ir(Ⅲ) CCC pincer complexes(SNHC-Ir, 1a–1c) is successfully designed and synthesized by developing a one-step methodology, which involves an initial coordination of Ir(I) with the NHC and subsequent metallation of double sp2C–H bonds. This method is considerably useful over those reported by using strong coordination ligand or carbonic anion exchange,and would provide an alternative efficient template of organometallics synthesis. Experimental and density functional theory(DFT) calculation results indicate that the spirocyclic framework is a favourable factor for the facile formation and stabilization of these complexes. Primary investigation shows that chloride 1b can well catalyze homo and hetero addition of styrene derivatives and remote olefin isomerization, which represents the first catalytic application of the dianionic CCC pincer complexes.展开更多
基金This work was supported by the National Natural Science Foundation of China(21502080,21772076,21871117,21772071,21702136,91956203)the“111”Program of Ministry of Education of China,the Major Project(2018ZX09711001-005-002)of Ministry of Science and Technology of China+2 种基金the Science and Technology Commission of Shanghai Municipality(19IC1430100)This work was supported by the High-Performance Computing Center of Shanghai Jiao Tong UniversityAlso,we thank Prof.Qing-Wei Zhang from the University of Science and Technology of China for his helpful discussion.
文摘A new type of dianionic Ir(Ⅲ) CCC pincer complexes(SNHC-Ir, 1a–1c) is successfully designed and synthesized by developing a one-step methodology, which involves an initial coordination of Ir(I) with the NHC and subsequent metallation of double sp2C–H bonds. This method is considerably useful over those reported by using strong coordination ligand or carbonic anion exchange,and would provide an alternative efficient template of organometallics synthesis. Experimental and density functional theory(DFT) calculation results indicate that the spirocyclic framework is a favourable factor for the facile formation and stabilization of these complexes. Primary investigation shows that chloride 1b can well catalyze homo and hetero addition of styrene derivatives and remote olefin isomerization, which represents the first catalytic application of the dianionic CCC pincer complexes.
