title: Transient intermediates from Mn(salen) with sterically hindered mesityl groups: interconversion between MnIV-phenolate and MnIII-phenoxyl radicals as an origin for unique reactivity.
abstract: In order to reveal structure-reactivity relationships for the high catalytic activity of the epoxidation catalyst Mn(salen), transient intermediates are investigated. Steric hindrance incorporated to the salen ligand enables highly selective generation of three related intermediates, OMnIV(salen), HO-Mn IV(salen), and H2O-MnIII(salen (+*)), each of which is thoroughly characterized using various spectroscopic techniques including UV-vis, electron paramagnetic resonance, resonance Raman, electrospray ionization mass spectrometry, 2H NMR, and X-ray absorption spectroscopy. These intermediates are all one-electron oxidized from the starting MnIII(salen) precursor but differ only in the degree of protonation. However, structural and electronic features are strikingly different: The Mn-O bond length of HO-MnIV(salen) (1.83 A) is considerably longer than that of OMnIV(salen) (1.58 A); the electronic configuration of H2O-MnIII(salen (+*)) is MnIII-phenoxyl radical, while those of OMnIV(salen) and HO-MnIV(salen) are MnIV-phenolate. Among OMnIV(salen), HO-MnIV(salen), and H2O-MnIII(salen (+*)), only the OMnIV(salen) can transfer oxygen to phosphine and sulfide substrates, as well as abstract hydrogen from weak C-H bonds, although the oxidizing power is not enough to epoxidize olefins. The high activity of Mn(salen) is a direct consequence of the favored formation of the reactive OMnIV(salen) state.
authors.affiliation: Institute for Molecular Science & Okazaki Institute for Integrative Bioscience, National Institutes of Natural Sciences, Myodaiji, Okazaki, Aichi 444-8787, Japan.
authors.forename: Takuya
authors.initials: T
authors.lastname: Kurahashi
authors.forename: Akihiro
authors.initials: A
authors.lastname: Kikuchi
authors.forename: Takehiko
authors.initials: T
authors.lastname: Tosha
authors.forename: Yoshitsugu
authors.initials: Y
authors.lastname: Shiro
authors.forename: Teizo
authors.initials: T
authors.lastname: Kitagawa
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Fujii
mesh_terms: D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D017895:Manganese Compounds / Q000737:chemistry*; D015394:Molecular Structure; D010636:Phenols / Q000737:chemistry*; D013059:Spectrum Analysis, Raman
chemical_list: D017895:Manganese Compounds; D010636:Phenols