A hydroperoxorhodium complex: Oxidation of the coordinated triphenylphosphine

Suzuki, Hiroharu; Matsuura, Shinji; Moro‐oka, Yoshihiko; Ikawa, Tsuneo

doi:10.1016/0022-328x(85)88011-6

Cited by 38 publications

(13 citation statements)

References 18 publications

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“…Hydroperoxide ion has been shown to be involved in the oxidation of phosphines by oxygen catalyzed by Pt(PPh 3 ) 2 (O 2 ) . Intramolecular O-transfer from peroxo groups to coordinated phosphines to generate phosphine oxides has been reported for complexes such as RhCl(OOH)(acac)(PPh 3 ) 2 and RhCl(O 4 C)(PEt 2 Ph) 3 . Formation of peroxide complexes from the reactions of metal alkyls or hydrides with O 2 and production of H 2 O 2 from H 2 and O 2 catalyzed by transition-metal complexes has been reported .…”

Section: Resultsmentioning

confidence: 99%

Dioxygen Complexes from the Reactions of [Cp*RuH₂(PP)]⁺ (PP = dppm, dppe) with Air

Jia

Chu

et al. 1999

Organometallics

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Exposure of [Cp*RuH2(dppm)]BF4 in acetone or methanol to air produced a mixture of [Cp*Ru(O2)(dppm)]BF4 and [Cp*Ru(O2)(Ph2PCH2P(O)Ph2)]BF4. Reaction of Cp*RuCl(dppm) with NaBPh4 in methanol in air produced the dioxygen complex [Cp*Ru(O2)(dppm)]BPh4, which has been characterized by X-ray diffraction. Reaction of Cp*RuCl(dppm) with H2O2 in the presence of NaBPh4 in air produced [Cp*Ru(O2)(Ph2PCH2P(O)Ph2)]BPh4 and Ph2P(O)CH2P(O)PPh2. Reaction of [Cp*RuH2(dppe)]BF4 in acetone or methanol with air also produced a mixture of [Cp*Ru(O2)(dppe)]BF4 and [Cp*Ru(O2)(Ph2PCH2CH2P(O)Ph2)]BF4.

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Section: Resultsmentioning

confidence: 99%

Dioxygen Complexes from the Reactions of [Cp*RuH₂(PP)]⁺ (PP = dppm, dppe) with Air

Jia

Chu

et al. 1999

Organometallics

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“…Kinetic studies of stoichiometric phosphine oxidations, particularly on a series of isolable monomeric alkylperoxymetal compounds, are surprisingly rare even though a range of mechanisms are conceivable (and proposed in related metal−alkylperoxide systems), including radical chains via O−O bond homolysis to give alkoxyradical intermediates, 27 nucleophilic attack of the phosphine on an η 2 -peroxyzinc, and coordination of phosphine to zinc followed by nucleophilic attack by the alkylperoxide. 28,29 Reaction rates for To M ZnOOt-Bu and PR 3 follow the trend PPh 3 < P(p-C 6 H 4 Me) 3 < PMe 3 < PH 2 Ph; PPh 3 reacts in less than 2 h at 60°C, whereas PMe 3 reacts in less than 5 min at ambient temperature. The second-order rate law −d- Eyring analysis of the reaction between 8 and P(p-C 6 H 4 Me) 3 provides ΔH ‡ = 9.5 ± 0.3 kcal·mol −1 and ΔS ‡ = −27 ± 1 cal·mol…”

Section: Mechanistic Investigations and Kinetics Ofmentioning

confidence: 95%

Remarkably Robust Monomeric Alkylperoxyzinc Compounds from Tris(oxazolinyl)boratozinc Alkyls and O₂

2012

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Metal alkylperoxides are remarkable, highly effective, yet often thermally unstable, oxidants that may react through a number of possible pathways including O-O homolytic cleavage, M-O homolytic cleavage, nucleophilic O-atom transfer, and electrophilic O-atom transfer. Here we describe a series of zinc alkyl compounds of the type ToMZnR (ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate; R = Et, n-C3H7, i-C3H7, t-Bu) that react with O2 at 25 °C to form isolable monomeric alkylperoxides ToMZnOOR in quantitative yield. The series of zinc alkylperoxides is crystallographically characterized, and the structures show systematic variations in the Zn-O-O angle and O-O distances. The observed rate law for the reaction of ToMZnEt (2) and O2 is consistent with a radical chain mechanism, where the rate-limiting SH2 step involves the interaction of •OOR and ToMZnR. In contrast, ToMZnH and ToMZnMe are unchanged even to 120 °C under 100 psi of O2 and in the presence of active radical chains (e.g., •OOEt). This class of zinc alkylperoxides is unusually thermally robust, in that the compounds are unchanged after heating at 120 °C in solution for several days. Yet, these compounds are reactive as oxidants with phosphines. Additionally, an unusual alkylperoxy group transfer to organosilanes affords ToMZnH and ROOSiR3′. OOEt). This class of zinc alkylperoxides is unusually thermally robust, in that the compounds are unchanged after heating at 120°C in solution for several days. Yet, these compounds are reactive as oxidants with phosphines. Additionally, an unusual alkylperoxy group transfer to organosilanes affords To M ZnH and ROOSiR 3 ′.

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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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A hydroperoxorhodium complex: Oxidation of the coordinated triphenylphosphine

Cited by 38 publications

References 18 publications

Dioxygen Complexes from the Reactions of [Cp*RuH₂(PP)]⁺ (PP = dppm, dppe) with Air

Dioxygen Complexes from the Reactions of [Cp*RuH₂(PP)]⁺ (PP = dppm, dppe) with Air

Remarkably Robust Monomeric Alkylperoxyzinc Compounds from Tris(oxazolinyl)boratozinc Alkyls and O₂

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

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A hydroperoxorhodium complex: Oxidation of the coordinated triphenylphosphine

Cited by 38 publications

References 18 publications

Dioxygen Complexes from the Reactions of [Cp*RuH2(PP)]+ (PP = dppm, dppe) with Air

Dioxygen Complexes from the Reactions of [Cp*RuH2(PP)]+ (PP = dppm, dppe) with Air

Remarkably Robust Monomeric Alkylperoxyzinc Compounds from Tris(oxazolinyl)boratozinc Alkyls and O2

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

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Product

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Dioxygen Complexes from the Reactions of [Cp*RuH₂(PP)]⁺ (PP = dppm, dppe) with Air

Dioxygen Complexes from the Reactions of [Cp*RuH₂(PP)]⁺ (PP = dppm, dppe) with Air

Remarkably Robust Monomeric Alkylperoxyzinc Compounds from Tris(oxazolinyl)boratozinc Alkyls and O₂