Synthesis, characterization and reactivity of non-heme 1st row transition metal-superoxo intermediates

Noh, Hyeonju; Cho, Jaeheung

doi:10.1016/j.ccr.2018.12.006

Cited by 57 publications

(50 citation statements)

References 173 publications

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“…The solid state spectrum of 3 shows a isotope sensitive feature assigned as an O-O stretch which appears at 1045 cm −1 upon labeling, similar to other published vibrational data for superoxo species. [37][38][39][40][41][42][43][44][45][46][47][48][49] The feature with natural abundance O2 is difficult to directly assign due to overlap with other features in that area, but is likely underneath a feature at ~1105 cm −1 ( Figure S26) to give a shift of 60 cm −1 that is within experimental error of the predicted shift of 64 cm −1 from a simple harmonic oscillator approximation. In an effort to obtain a better subtraction dataset, the IR spectrum of 3 was also recorded as a C6H6 solution.…”

Section: Formation and Characterization Of A Ni Superoxide Complexmentioning

confidence: 60%

“…These values are consistent with other reported Ni(II) superoxo complexes. [37][38][39][40][41][42][43][44][45][46][47][48][49] We have extensively attempted to collect Raman data on 3 with no success. We have been, however, able to record infrared (IR) spectra of 3 as a KBr pellet and in solution with both 16 O2 and 18 O2.…”

Section: Formation and Characterization Of A Ni Superoxide Complexmentioning

confidence: 99%

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Generation and Oxidative Reactivity of a Ni(II) Superoxo Complex via Ligand-Based Redox Non-Innocence

McNeece¹,

Jesse²,

Xie³

et al. 2020

Preprint

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Metal ligand cooperativity is a powerful strategy in transition metal chemistry. This type of mechanism for the activation of O2 is best exemplified by heme centers in biological systems. While aerobic oxidations with Fe and Cu are well precedented, Ni-based oxidations are frequently less common due to less-accessible metal-based redox couples. Some Ni enzymes utilize special ligand environments for tuning the Ni(II)/(III) redox couple such as strongly donating thiolates in Ni superoxide dismutase. A recently characterized example of a Ni-containing protein, however, suggests an alternative strategy for mediating redox chemistry with Ni by utilizing ligand-based reducing equivalents to enable oxygen binding. While this mechanism has little synthetic precedent, we show here that Ni complexes of the redox-active ligand tBu,TolDHP (tBu,TolDHP = 2,5-bis((2-t-butylhydrazono)(p-tolyl)methyl)-pyrrole) activate O2 to generate a Ni(II) superoxo complex via ligand-based electron transfer. This superoxo complex is competent for stoichiometric oxidation chemistry with alcohols and hydrocarbons. This work demonstrates that coupling ligand-based redox chemistry with functionally redox-inactive Ni centers enables oxidative transformations more commonly mediated by metals such as Fe and Cu.

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Section: Formation and Characterization Of A Ni Superoxide Complexmentioning

confidence: 60%

Section: Formation and Characterization Of A Ni Superoxide Complexmentioning

confidence: 99%

Generation and Oxidative Reactivity of a Ni(II) Superoxo Complex via Ligand-Based Redox Non-Innocence

McNeece¹,

Jesse²,

Xie³

et al. 2020

Preprint

View full text Add to dashboard Cite

show abstract

“…[15] The distortion in octahedral geometry is due to the bulky chelation of ligand towards transitions metal ion. The coordination mode of bipyridine (N-donor ligand), 3,4-dichlorophenylactate (O-donor ligand) and water molecule towards copper(II) ion results mononuclear complex with a distorted octahedral arrangement (1). The chelating mode of bipyridine (N-donor ligand), biphen- ylactate (O-donor ligand) leads to strong distorted octahedral geometry due to the presence of a bulky ligand (biphenylactate) (2).…”

Section: Structural Descriptionmentioning

confidence: 99%

“…The structural variation depends upon the coordination mode of metal ion, the nature of ligand (Lewis base) and solvent system. The variation in nuclearity and coordination number of the complex is governed by metal ion as well as the attached ligands , …”

Section: Introductionmentioning

confidence: 99%

“…The variation in nuclearity and coordination number of the complex is governed by metal ion as well as the attached ligands. [1,2] Transition metals such as copper and zinc are most valuable metals because of the ability to form mixed ligand complexes. It has been found that most of the Cu II and Zn II complexes are found in octahedral and square pyramidal arrangement while the nuclearities are extended from mononuclear to polynuclear.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Characterization, Structural Description, Micellization Behavior, DNA Binding Study and Antioxidant Activity of 4, 5 and 6‐Coordinated Copper(II) and Zinc(II) Complexes

Iqbal

Karim

Ali

et al. 2020

Zeitschrift anorg allge chemie

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Four mononuclear copper(II) and zinc(II) complexes were synthesized by the reaction of copper and zinc salts with 3,4‐dichlorophenylactic acid, 2‐bromophenylactic acid, biphenylacetic acid (O‐donor ligand) and bipyridine (N‐donor ligands) having the general formulae [(L)2Cu(bp)(H2O)] (1), [(BpA)2Cu(bp)] (2), [(L)2Zn(bp)(H2O)] (3) and [(L*)2Zn(bp)] (4) (L = 3,4‐dichlorophenylacetate, L* = 2‐bromophenylacetate bp = bipyridine, and BpA = biphenylacetate). Structures of all compounds were characterized through FT‐IR spectroscopy and X‐ray diffraction analysis. FT‐IR spectra of all complexes confirmed the binding mode of Cu‐O and Zn‐O. XRD data revealed that complexes 1–3 exhibited distorted octahedral arrangement, whereas complex 4 has a distorted tetrahedral environment. Micellization behavior was examined with anionic surfactant (SDS) by conductance measurement as well as absorption spectral analysis. DNA binding study was assessed through viscosity measurement and UV/Vis spectrophotometry. DPPH free radical scavenging assay was measured by UV/Vis spectrophotometry. The results showed nice biological potential of all the complexes.

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Structure and Unprecedented Reactivity of a Mononuclear Nonheme Cobalt(III) Iodosylbenzene Complex

et al. 2020

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A mononuclear nonheme cobalt(III) iodosylbenzene complex, [CoIII(TQA)(OIPh)(OH)]2+ (1), is synthesized and characterized structurally and spectroscopically. While 1 is a sluggish oxidant in oxidation reactions, it becomes a competent oxidant in oxygen atom transfer reactions, such as olefin epoxidation, in the presence of a small amount of proton. More interestingly, 1 shows a nucleophilic reactivity in aldehyde deformylation reaction, demonstrating that 1 has an amphoteric reactivity. Another interesting observation is that 1 can be used as an oxygen atom donor in the generation of high‐valent metal‐oxo complexes. To our knowledge, we present the first crystal structure of a CoIII iodosylbenzene complex and the unprecedented reactivity of metal‐iodosylarene adduct.

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Synthesis, characterization and reactivity of non-heme 1st row transition metal-superoxo intermediates

Cited by 57 publications

References 173 publications

Generation and Oxidative Reactivity of a Ni(II) Superoxo Complex via Ligand-Based Redox Non-Innocence

Generation and Oxidative Reactivity of a Ni(II) Superoxo Complex via Ligand-Based Redox Non-Innocence

Synthesis, Characterization, Structural Description, Micellization Behavior, DNA Binding Study and Antioxidant Activity of 4, 5 and 6‐Coordinated Copper(II) and Zinc(II) Complexes

Structure and Unprecedented Reactivity of a Mononuclear Nonheme Cobalt(III) Iodosylbenzene Complex

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