Multicopper complexes and coordination polymers for mild oxidative functionalization of alkanes

Kirillov, Alexander M.; Kirillova, Marina V.; Pombeiro, Armando J. L.

doi:10.1016/j.ccr.2012.07.022

Cited by 198 publications

(131 citation statements)

References 90 publications

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“…A variety of multicopper catalysts for hydrocarbon oxidations have been described [366,367], but while stable Cu(I) or Cu(II) precursors or 'resting states' are often identified, the nature of the multicopper-oxygen intermediates responsible for attacking the C-H bonds are usually only speculated on the basis of indirect and/or ambiguous spectroscopic or theoretical evidence [368][369][370]. In studies of dioxygen activation by more than two Cu(I) sites that target possible intermediates, tricopper species often comprise the bis(μ-oxo)tricopper(II,II,III) core (114, Figure 53).…”

Section: Tricopper Models Of Multicopper Active Sites In Enzymesmentioning

confidence: 99%

Transition Metal Complexes and the Activation of Dioxygen

Yee

Tolman

2014

Metal Ions in Life Sciences

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In order to address how diverse metalloprotein active sites, in particular those containing iron and copper, guide O₂binding and activation processes to perform diverse functions, studies of synthetic models of the active sites have been performed. These studies have led to deep, fundamental chemical insights into how O₂coordinates to mono- and multinuclear Fe and Cu centers and is reduced to superoxo, peroxo, hydroperoxo, and, after O-O bond scission, oxo species relevant to proposed intermediates in catalysis. Recent advances in understanding the various factors that influence the course of O₂activation by Fe and Cu complexes are surveyed, with an emphasis on evaluating the structure, bonding, and reactivity of intermediates involved. The discussion is guided by an overarching mechanistic paradigm, with differences in detail due to the involvement of disparate metal ions, nuclearities, geometries, and supporting ligands providing a rich tapestry of reaction pathways by which O₂is activated at Fe and Cu sites.

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Section: Tricopper Models Of Multicopper Active Sites In Enzymesmentioning

confidence: 99%

Transition Metal Complexes and the Activation of Dioxygen

Yee

Tolman

2014

Metal Ions in Life Sciences

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“…In view of the well recognized biological function of copper, which is present in the active sites of many oxidation enzymes, several complexes were prepared and used as catalyst while the oxide source was hydrogen peroxide. 56 The dehydrogenation of n-hexane and cycloalkanes, giving n-hexene and cycloalkenes, was observed in the reaction of such hydrocarbons with hydrogen peroxide in the presence of copper complexes bearing trispyrazolylborate ligands. Experimental data exclude the participation of hydroxyl radicals derived from Fenton-like reaction mechanisms.…”

Section: Oxidation Of Alkanesmentioning

confidence: 99%

Synthetic utility of metal catalyzed hydrogen peroxide oxidation of C-H, C-C and C=C bonds in alkanes, arenes and alkenes: Recent advances

Wójtowicz‐Młochowska¹

2016

Arkivoc

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This review presents the current state of the art of homogenic and heterogenic oxygen transfer processes using hydrogen peroxide as oxygen source and compounds and complexes of tranisition metals, Fe, V, Cu, Mn, Rh, Mo, Ti, W, Pd, Os, Zr, Cr, Nb, Co, as the catalysts. Based on the reactions of C-H, C-C and C=C bonds in alkanes, arenes and alkenes various mechanisms of the oxygen-transfer processes are discussed and new methodologies for synthesis of alcohols, phenols, aldehydes, ketones, epoxides and carboxylic acids are indicated.

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“…This interest stems from their potential applications as functional materials such as gas storage, ion exchangers, catalysis, magnetism, and molecular sensing [22][23][24][25][26][27][28]. These compounds containing redox active ions of transition metals such as Fe, Co, Ni, Cu, Mn, Mo and V may have catalytic activity for reactions following a redox mechanism [29].…”

Section: Introductionmentioning

confidence: 99%

Investigation of the catalytic behavior of a Cu coordination polymer capped polyoxometalate as an oxidation catalyst

Farzaneh

Moghzi

2015

Reac Kinet Mech Cat

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A multifunctional organic-inorganic hybrid based on a Cu coordination polymer capped polyoxometalate (H 3 PMo 12 O 40 ) designated as compound 1 with [Cu I (4,4 0 -bipy)] 3 [PMo 10 VI Mo 2 V O 40 {Cu II (2,2 0 -bipy)}] formula was prepared using CuCl 2 Á2H 2 O, 4,4 0 -bipy, 2,2 0 -bipy and H 3 PMo 12 O 4 in water under hydrothemal conditions. The prepared compound 1 was characterized by FTIR, XRD and chemical analysis techniques. It was found that the compound successfully catalyzes the epoxidation of various alkenes such as diphenyl ethylene, trans-stilbene, cyclohexene, norbornene, styrene and cyclooctene and oxidation of alkanes such as fluorene, adamantane, diphenylmethane, cyclohexane and cyclooctane, in acetonitrile with 20-99 % conversion and 53-100 % selectivity with tert-butyl hydroperoxide as oxidant under optimized condition. This heterogeneous catalyst could be easily recovered and reused after reaction without loss of activity.

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Multicopper complexes and coordination polymers for mild oxidative functionalization of alkanes

Cited by 198 publications

References 90 publications

Transition Metal Complexes and the Activation of Dioxygen

Transition Metal Complexes and the Activation of Dioxygen

Synthetic utility of metal catalyzed hydrogen peroxide oxidation of C-H, C-C and C=C bonds in alkanes, arenes and alkenes: Recent advances

Investigation of the catalytic behavior of a Cu coordination polymer capped polyoxometalate as an oxidation catalyst

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