Intramolecular Electron Transfer from Mn or Ligand Phenolate to Photochemically Generated RuIII in Multinuclear Ru/Mn Complexes. Laser Flash Photolysis and EPR Studies on Photosystem II Models

作者: Dirk Burdinski , Karl Wieghardt , Steen Steenken

DOI: 10.1021/JA991402D

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摘要: In a mononuclear MnIV and trinuclear MnII complex, the ligands of which contain electron-rich phenols (coordinated to Mn('s)) covalently attached ruthenium(II) 2,2‘-trisbipyridyl(=bpy)-type groups, intramolecular electron transfer (ET) from phenolate ligand (in complex) or photochemically (λexc= 455 nm) generated RuIII takes place with k ≥ 5 × 107 s-1, giving rise corresponding phenoxyl radical (complexed MnIV) MnIII, respectively. Thus, in source that reduces photogenerated RuIII(bpy•-) moiety is MnII, contrast situation where stems phenolate. The half-life coordinated phenoxyl-type Ru(bpy)/Mn complex (as produced presence [CoIII(NH3)5Cl]2+) order 0.5−1 ms. Ru(bpy) compound containing three (phenolate-ligated) atoms first example photoche...

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