【摘 要】
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The diastereoselective photoreactions of Ir(Ⅲ)-amine and Ir(Ⅲ)-diamine complexes are observed in the presence of O2.The∧-[Ir(pq)2(R-mapy)](PF6) (pq is 2-phenylquinoline and mapy is 2-(1-aminoethyl)pyridine) diastereomer is dehydrogenatively oxidized into
【机 构】
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MOE Key Laboratory of Bioinorganic and Synthetic Chemistry,School of Chemistry,Sun Yat-sen Universit
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The diastereoselective photoreactions of Ir(Ⅲ)-amine and Ir(Ⅲ)-diamine complexes are observed in the presence of O2.The∧-[Ir(pq)2(R-mapy)](PF6) (pq is 2-phenylquinoline and mapy is 2-(1-aminoethyl)pyridine) diastereomer is dehydrogenatively oxidized into imine complex ∧-[Ir(pq)2(mapy-2H)](PF6) at room temperature,while the ∧-[Ir(pq)2(S-mapy)](PF6) diastereomer occurs interlig-and C—N cross-coupling reaction at 60 ℃,affording a new tetradentate complex ∧-[Ir(pq)(S-pqpe)](PF6) (pqpe is 2-phenyl-N-(1-pyri-din-2-yl)ethyl-quinolin-8-amine).The identical cases are also observed in diamine complexes ∧-[Ir(pq)2(R,R-chda)](PF6) (chda is 1,2-diaminocyclohexane),∧-[Ir(pq)2(R,S-chda)](PF6),and ∧-[Ir(pq)2(S,S-chda)](PF6),where the R configuration ligand is dehydrogena-tively oxidized into imine,while the S configuration is retentive and the bound nitrogen atom is coupling to the C8 of pq ligand,af-fording ∧-[Ir(pq)2(chdi)](PF6) (chdi is 1,2-diiminocyclohexane),∧-[Ir(pq)(S-pqchim)](PF6) (pqchim is N-(2-iminocyclohexyl)-2-phenyl-quinolin-8-amine),and ∧-[Ir(S,S-pqchda)](PF6) (pqchda is N\',N\"-bis(2-phenylquinolin-8-yl)cyclohexane-1,2-diamine),respectively.These provide a new and useful protocol for the synthesis of multidentate ligands in situ via the postcoordinated interligand-coupling strategy under mild conditions.
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