Synthesis, characterization and molecular structure of the hydroperoxo complex [(η5C5Me5)Ir(µ-pz)3Rh(OOH)(dppe)][BF4]; Hpz = pyrazole, dppe β 1,2-bis(diphenylphosphino)ethane

Carmona, Daniel; Lamata, M. Pilar; Ferrer, Joaquina; Modrego, Jávier; Perales, Martin; Lahoz, Fernando J.; Atencio, Reinaldo; Oro, Luis A.

doi:10.1039/c39940000575

Cited by 50 publications

(40 citation statements)

References 16 publications

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“…The most widely known metal peroxides are the T| 2 -peroxo complexes. Transition metals which form side-on dioxygen complexes include: l87eg Ti, V, Nb, Cr, Mo, W, Fe, 188 Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, and U. Mononuclear r|'-dioxygen metal complexes are believed to be formed with Co, 189 Cr, 190 Fe, 96 Rh, 191 Ir, 192 and Sm. 193 Metal-peroxo complexes can react with both electrophilic and nucleophilic substrates although not all peroxo complexes are reactive.…”

Section: Transition Metal Peroxidesmentioning

confidence: 98%

Biomimetic Oxygenations Related to Cytochrome P450: Metal-Oxo and Metal-Peroxo Intermediates

McLain

Lee

Groves

2000

Biomimetic Oxidations Catalyzed by Transition Metal Complexes

123

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Oxometalloporphyrin Intermediates in Enzymatic ProcessesMetalloenzymes catalyze a host of biological oxidation reactions that are crucial to life processes. The cytochromes P450, an important family of heme-iron metalloenzymes, are oxidoreductases that activate molecular oxygen (O2) and incorporate one of the oxygen atoms into a wide variety of biological substrates, with concurrent two-electron reduction of the other oxygen atom to H 2 0.' The structure, biochemistry, molecular biology and the chemistry of cytochrome P450 and related model systems was extensively reviewed recently. 1 Cytochrome P450 enzymes have been isolated from numerous mammalian tissues (e.g. liver, kidney, lung, intestine and adrenal cortex), as well as insects, plants, yeast and bacteria, 2 and are known to catalyze hydroxylations, epoxidations, N-, S-and O-dealkylations, N-oxidations, sulfoxidations, and dehalogenations. 1 These oxygenation reactions play a central role in carcinogen activation, drug and xenobiotic detoxification, and steroid and prostaglandin metabolism. Surprisingly, the active site of the enzyme, known in detail from several X-ray crystal structures, is extraordinarily simple, with an iron protoporphyrin IX (3.1; Fig. 3.1) buried deep in a hydrophobic, substrate-binding pocket of 91 Biomimetic Oxidations Catalyzed by Transition Metal Complexes Downloaded from www.worldscientific.com by KAINAN UNIVERSITY on 02/20/15. For personal use only.

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Section: Transition Metal Peroxidesmentioning

confidence: 98%

Biomimetic Oxygenations Related to Cytochrome P450: Metal-Oxo and Metal-Peroxo Intermediates

McLain

Lee

Groves

2000

Biomimetic Oxidations Catalyzed by Transition Metal Complexes

123

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“…Furthermore, the Raman spectrum of 6 a shows an absorption band at 1624 cm −1 for the formato ligand. Another band at 859 cm −1 shifts to 815 cm −1 for the 18 O‐labeled isotopologue 6 b (Δ${\tilde \nu }$ =44 cm −1 ) and can be assigned to the OOH stretching vibration 12a. 19…”

Section: Methodsmentioning

confidence: 99%

Hydrogenation of a Rhodium Peroxido Complex by Formate Derivatives: Mechanistic Studies and the Catalytic Formation of H₂O₂ from O₂

Meier

Braun

2012

Angewandte Chemie

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“…In the following sections we focus on model reactions for the oxygenation of olefin complexes. We should mention here that several rhodium–peroxo106, 107 and –hydroperoxo108–111 complexes have been reported, including a crystallographically characterized hydroperoxo–rhodium( III ) complex obtained by the reaction of a rhodium( I ) complex with O 2 and H + 108. A related topic, dioxygen binding and activation at cobalt, was reviewed by Bianchini and Zoellner 105…”

Section: Stoichiometric Models For Oxidation Catalysismentioning

confidence: 97%

Functional Models for Rhodium‐Mediated Olefin‐Oxygenation Catalysis

2004

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Oxygenation of C-H and C=C bonds of hydrocarbons with H2O2 and O2 is an important industrial method to convert mineral oil into useful chemicals. Despite their enormous economic impact, these reactions are still not fully understood. In the early 1970s, the potential of Rh and Ir complexes for olefin oxygenation was investigated intensively. Simple inorganic salts of these metals proved to be rather useless for industrial application when compared with the traditional Wacker system. However, the appropriate choice of ligands allows the stepwise oxidation of olefins at Rh and Ir. These systems are therefore useful to study mechanistic details of substrate binding and C-O bond formation at the catalytic metal center. Insight from these model studies helps in understanding the catalytic reactions at these (and possibly other) metal centers. Further insight into the differences between the Rh system and traditional Wacker-type oxidation at Pd may lead to useful applications.

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Synthesis, characterization and molecular structure of the hydroperoxo complex [(η⁵C₅Me₅)Ir(µ-pz)₃Rh(OOH)(dppe)][BF₄]; Hpz = pyrazole, dppe β 1,2-bis(diphenylphosphino)ethane

Cited by 50 publications

References 16 publications

Biomimetic Oxygenations Related to Cytochrome P450: Metal-Oxo and Metal-Peroxo Intermediates

Biomimetic Oxygenations Related to Cytochrome P450: Metal-Oxo and Metal-Peroxo Intermediates

Hydrogenation of a Rhodium Peroxido Complex by Formate Derivatives: Mechanistic Studies and the Catalytic Formation of H₂O₂ from O₂

Functional Models for Rhodium‐Mediated Olefin‐Oxygenation Catalysis

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Synthesis, characterization and molecular structure of the hydroperoxo complex [(η5C5Me5)Ir(µ-pz)3Rh(OOH)(dppe)][BF4]; Hpz = pyrazole, dppe β 1,2-bis(diphenylphosphino)ethane

Cited by 50 publications

References 16 publications

Biomimetic Oxygenations Related to Cytochrome P450: Metal-Oxo and Metal-Peroxo Intermediates

Biomimetic Oxygenations Related to Cytochrome P450: Metal-Oxo and Metal-Peroxo Intermediates

Hydrogenation of a Rhodium Peroxido Complex by Formate Derivatives: Mechanistic Studies and the Catalytic Formation of H2O2 from O2

Functional Models for Rhodium‐Mediated Olefin‐Oxygenation Catalysis

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Resources

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Synthesis, characterization and molecular structure of the hydroperoxo complex [(η⁵C₅Me₅)Ir(µ-pz)₃Rh(OOH)(dppe)][BF₄]; Hpz = pyrazole, dppe β 1,2-bis(diphenylphosphino)ethane

Hydrogenation of a Rhodium Peroxido Complex by Formate Derivatives: Mechanistic Studies and the Catalytic Formation of H₂O₂ from O₂