A functional model for pMMO (particulate methane monooxygenase): Hydroxylation of alkanes with H2O2 catalyzed by β-diketiminatocopper(II) complexes

Efficient catalytic oxidation of hydrocarbons mediated by tricopper clusters under mild conditions

“…These systems are mostly based on Cu II complexes, whereas the present tricopper catalysts are Cu I Cu I Cu I complexes that are activated by H 2 O 2 to allow one of the copper ions to become formally Cu III . Interestingly, Itoh and coworkers [28] have reported hydroxylation of alkanes with H 2 O 2 catalyzed by b-diketiminatocopper(II) complexes with similar efficiency to the tricopper system that we have described here and have suggested that the active oxygen intermediate might be a Cu III species as well. A number of structurally characterized Cu II Cu II Cu III and Cu II Cu II Cu II complexes upon oxygen activation of the corresponding reduced copper complexes have also appeared over the years [29,30].…”

Aromatic Hydroxylation Reactivity of a Mononuclear Cu(II)−Alkylperoxo Complex

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] Several types of mononuclear and dinuclear copper/active-oxygen complexes have been reported, and their structures and physicochemical properties have been explored in detail. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] However, less is known about the intrinsic reactivity of the generated copper/ active-oxygen complexes.We herein report a new copper(II)-alkylperoxo species 2 X [2-hydroxy-2-hydroperoxypropane (HHPP) adduct], which is generated by the reaction of H 2 O 2 and copper(II) complex 1 X supported by the bis(pyridylmethyl)amine tridentate ligand containing msubstituted phenyl groups at the 6-positions of the pyridine rings (L X ) in acetone in the presence of triethylamine (NEt 3 ) (Scheme 1). The alkylperoxo intermediate 2 X undergoes an efficient aromatic ligand hydroxylation reaction, producing phenolate complex 4 X via another intermediate 3 X .…”

“…If 2 NO 2 were instead to be a copper(II)-hydroperoxo species, Cu(II)-OOH, the Raman spectrum should be much simpler, showing only one peak near 800 cm -1 due to the O-O bond stretching vibration. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] A plausible structure of copper(II)-alkylperoxo complex 2 NO 2 is a 2-hydroxy-2-hydroperoxypropane (HHPP) adduct as indicated in Scheme 1. A similar HHPP adduct of iron(III) has recently been reported by Que and co-workers in the reaction of Fe II (TPA) and H 2 O 2 in acetone.…”

Copper(II) coordination polymers derived from triethanolamine and pyromellitic acid for bioinspired mild peroxidative oxidation of cyclohexane

“…It bears an active site composed of a multinuclear Cu cluster possessing a NO-environment [14][15][16]. However, although numerous examples of bioinspired copper compounds have been reported [10][11][12]17,18], the synthetic and catalytic (with respect to alkanes) studies on multinuclear copper complexes related to pMMO remain rather scant [19][20][21][22][23].…”