Selective catalytic oxidation of hydrocarbons. New prospects

Although catalytic reductions, cross‐couplings, metathesis, and oxidation of CC double bonds are well established, the corresponding catalytic hydroxylations of CH bonds in alkanes, arenes, or benzylic (allylic) positions, particularly with O2, the cheapest, “greenest”, and most abundant oxidant, are severely lacking. Certainly, some promising examples in homogenous and heterogenous catalysis exist, as well as enzymes that can perform catalytic aerobic oxidations on various substrates, but these have never achieved an industrial‐scale, owing to a low space‐time‐yield and poor stability. This review illustrates recent advances in aerobic oxidation catalysis by discussing selected examples, and aims to stimulate further exciting work in this area. Theoretical work on catalyst precursors, resting states, and elementary steps, as well as model reactions complemented by spectroscopic studies provide detailed insight into the molecular mechanisms of oxidation catalyses and pave the way for preparative applications. However, O2 also poses a safety hazard, especially when used for large scale reactions, therefore sophisticated methodologies have been developed to minimize these risks and to allow convenient transfer onto industrial scale.

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“…turnover numbers TONs), stability, as well as selectivity, are still important issues in current research 8. 9…”

Section: Introductionmentioning

confidence: 99%

Selective Catalytic Oxidation of CH Bonds with Molecular Oxygen

et al. 2012

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“…Research of structure and catalytic activity of complexes of nickel in different reactions of oxidation with molecular O 2 has been causing heightened interest of researchers in the recent years due to the fact that nickel as an essential catalytic cofactor of enzymes is found in eubacteria, archaebacteria, fungi, and plants. These enzymes catalyze a diverse array of reactions that include both redox and nonredox chemistries [1,6].…”

Section: Introductionmentioning

confidence: 99%

Some Supramolecular Nanostructures Based on Catalytic Active Nickel and Iron Heteroligand Complexes. Functional Models of Ni(Fe) Dioxygenases

Matienko¹,

Binyukov²,

Mosolova³

et al. 2014

ChChT

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The possibility of the supramolecular nano structures formation on the basis of iron and nickel heteroligand complexes: Fe x (acac) y 18C6 m (H 2 O) n , and Fe x (acac) y (CTAB) p (H 2 O) q , or Ni 2 (OAc) 3 (acac)L 2 ·2H 2 O (L 2 = MP) − with the assistance of H-bonding, is researched using the AFM method. Formation of different supramolecular nanostructures on the basis of nickel and iron heteroligand complexes as models for Ni(Fe)ARD Dioxygenases may be used for understanding of different actions of these enzymes.

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“…Polyethylenes are typically not easily functionalized at specific positions in a post‐polymerization reaction . In addition, the options to arrive at terminally functional products during ethylene polymerization are limited because of the type of reagents that are compatible with the highly reactive olefin polymerization catalysts .…”

Section: Introductionmentioning

confidence: 99%

“…Polyethylenes are typically not easily functionalized at specific positions in a post-polymerization reaction. [1][2][3][4][5] In addition, the options to arrive at terminally functional products during ethylene polymerization are limited because of the type of reagents that are compatible with the highly reactive olefin polymerization catalysts. [6,7] Nevertheless, such end-functionalized poly-and oligo-ethylenes are highly useful for adapting the properties, especially the surface properties (chemically and physically), as such polymers with hydrophilic functional groups usually separate from the bulk.…”

Section: Introductionmentioning

confidence: 99%

Facile Synthesis of Hydroxyl‐Terminated Oligoethylenes

Meyer

Scholtyssek

Luinstra

2014

Macro Materials & Eng

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The synthesis of terminal hydroxyl-functionalized oligoethylene is achieved in a two-step one-pot method. Aluminum long chain alkyls (Al-PE) were generated by a catalytic chain transfer reaction involving iron 2,6-bis(imino)pyridyl ligation catalysts and methyl aluminoxane (MAO) aluminum alkyl precursors. At a high catalyst/cocatalyst ratio (>5 000) and a low ethylene pressure (1 bar) the chain transfer to aluminum is the dominant termination step. Discharging oxygen or dry air into the post polymerization reaction mixture leads to aluminum alkoxides (Al-O-PE) and after hydrolysis to hydroxyl-functionalized polyethylene (PE-OH). The degree of oxy-functionalization (up to 88 AE 3%) increased with increasing oxygen pressure and temperature and was more efficient with aluminum alkyls with a lower molecular weight.

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Selective catalytic oxidation of hydrocarbons. New prospects

Cited by 45 publications

References 97 publications

Selective Catalytic Oxidation of CH Bonds with Molecular Oxygen

Selective Catalytic Oxidation of CH Bonds with Molecular Oxygen

Some Supramolecular Nanostructures Based on Catalytic Active Nickel and Iron Heteroligand Complexes. Functional Models of Ni(Fe) Dioxygenases

Facile Synthesis of Hydroxyl‐Terminated Oligoethylenes

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