Mechanistic studies of alkene epoxidation catalyzed by nickel(II) cyclam complexes.  Oxygen-18 labeling and substituent effects

Kinneary, Joanne F.; Albert, Jeffrey S.; Burrows, Cynthia J.

doi:10.1021/ja00226a029

Cited by 118 publications

(35 citation statements)

References 3 publications

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“…Although Ni III -oxo compounds have never been directly detected, they have been proposed as key intermediates in some oxidation processes. [45][46][47] In fact, the appearance of transient 3 in oxidative transformations was also previously proposed by us for the oxidation of triphenylphosphine by 1. [22] Moreover, it has been computationally calculated that (b-diketiminato)-Ni III -oxo species could be good candidates for facile oxidation of methane.…”

supporting

confidence: 65%

Dioxygenase‐Like Reactivity of an Isolable Superoxo–Nickel(II) Complex

Yao

Ray

Drieß

2010

Chemistry A European J

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Although O(2) activation by metals such as iron and copper has been a matter of intensive research in the last decades, this type of chemistry for nickel systems is still in its infancy. Moreover, studies regarding the oxidizing ability of the resulting "Ni(n)-O(2)" species towards exogenous substrates are scarce. In this work, we report on the reactivity of an isolable and thermally stable mononuclear superoxo-nickel compound [Ni(II)(beta-diketiminato)(O(2))] (1) towards different types of organic substrates. In addition, we have been able to prove that the beta-diketiminato ligand can undergo partial intramolecular oxidation due to close proximity between the isopropyl groups of the beta-diketiminato-aryl and the superoxo subunits. Compound 1 performs hydrogen-atom abstraction from O-H and N-H groups and most importantly it shows an unprecedented dioxygenase-like reactivity in the oxidation of 2,4,6-tri-tert-butylphenol. The latter reaction most likely occurs through the mediation of a putative [Ni(III)-oxo] intermediate, affording an unprecedented oxidation product of the phenol that incorporates two oxygen atoms from a single O(2) subunit. Results presented herein provide evidence of the striking oxidizing ability of dioxygen-nickel species and further support the viability to use such systems as oxidation catalysts analogous to its heavy metal congener, palladium.

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supporting

confidence: 65%

Dioxygenase‐Like Reactivity of an Isolable Superoxo–Nickel(II) Complex

Yao

Ray

Drieß

2010

Chemistry A European J

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“…Nickel-oxo species have also been suggested in the reaction of related polyamine-nickel complexes with oxygen atom donors (54)(55)(56)(57)(58). We propose a mechanism for protein cross-linking that involves oxidation of tyrosine by the reactive nickel species (Scheme 1).…”

Section: Discussionmentioning

confidence: 99%

Determining Protein−Protein Interactions by Oxidative Cross-Linking of a Glycine-Glycine-Histidine Fusion Protein

Brown

Burlingame

et al. 1998

Biochemistry

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The Ni(II) complex of the tripeptide NH 2 -glycine-glycine-histidine-COOH (GGH) mediates efficient protein-protein cross-linking in the presence of oxidants such as oxone and monoperoxyphthalic acid (MMPP). Here we demonstrate that GGH fused to the amino terminus of a protein can still support cross-linking. The tripeptide was expressed at the amino terminus of ecotin, a dimeric macromolecular serine protease inhibitor found in the periplasm of Escherichia coli. In the presence of Ni(OAc) 2 and MMPP, GGH-ecotin is cross-linked to give a species that has an apparent molecular mass of a GGHecotin dimer with no observable protein degradation. The cross-linking reaction occurs between two ecotin proteins in a dimer complex. Furthermore, GGH-ecotin can be cross-linked to a serine protease target, trypsin, and the reaction is specific for proteins that interact with ecotin. The cross-linking reaction has been carried out on small peptides, and the reaction products have been analyzed by matrix-assisted laser desorption/ionization mass spectrometry. The target of the reaction is tyrosine, and the product is bityrosyl cross-links. The yield of the cross-linking is on the order of 15%. However, the reaction efficiency can be increased 4-fold by a single amino acid substitution in the carboxy terminus of ecotin that places an engineered tyrosine within 5 Å of a naturally occurring tyrosine. This cross-linking methodology allows for the protein cross-linking reagent to be encoded for at the DNA level, thus circumventing the need for posttranslational modification.

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“…The catalytic ability of nickel(II) macrocyclic complexes towards hydrocarbon oxidation has been well documented in the literature [22]. Some square-planar nickel(II) complexes of macrocyclic ligands such as cyclam and Schiff-base have been shown to act as catalysts for epoxidation of alkenes when PhIO or NaOCl was used as a terminal oxidant [23,24]. However, catalytic efficiency of these complexes remains inexplicable with regards to the general consideration of the systematic of the metal redox as a function of coordination environment and the nature of terminal oxidants.…”

Section: Anen 3 O 2 )} 2 R] (Clo 4 ) 4 and [{Ni(mentioning

confidence: 99%

Bis(macrocyclic)dinickel(II) complexes containing phenylene bridges between 13-membered triaza dioxa macrocyclic ligands: in-situ one pot template synthesis, characterization and catalytic oxidation of cyclohexene

Salavati‐Niasari

Bazarganipour

Norouzi

2006

Transition Met Chem

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A new series of bis(macrocyclic)dinickel(II) complexes containing phenylene bridges between 13-membered triaza dioxa macrocyclic subunits have been synthesized via in-situ One Pot Template Condensation (IOPTC) of nitrogen-nitrogen linker, CH 2 O and 1,8-diamino-3,6-dioxaoctane and nickel(II) in a 1:4:2:2 molar ratio. These complexes have been found to be effective catalysts for the selective oxidation of cyclohexene to 2-cyclohexene-1-one and 2-cyclohexene-2-ol with molecular oxygen as the oxidant.

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Mechanistic studies of alkene epoxidation catalyzed by nickel(II) cyclam complexes. Oxygen-18 labeling and substituent effects

Cited by 118 publications

References 3 publications

Dioxygenase‐Like Reactivity of an Isolable Superoxo–Nickel(II) Complex

Dioxygenase‐Like Reactivity of an Isolable Superoxo–Nickel(II) Complex

Determining Protein−Protein Interactions by Oxidative Cross-Linking of a Glycine-Glycine-Histidine Fusion Protein

Bis(macrocyclic)dinickel(II) complexes containing phenylene bridges between 13-membered triaza dioxa macrocyclic ligands: in-situ one pot template synthesis, characterization and catalytic oxidation of cyclohexene

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