Ligand Effects on the Chemical Activity of Copper(I) Complexes: Outer‐ and Inner‐Sphere Oxidation of Cu<sup>I</sup>L

Burg, Ariela; Maimon, Eric; Cohen, Haim; Meyerstein, Dan

doi:10.1002/ejic.200600702

Cited by 11 publications

(6 citation statements)

References 55 publications

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“…324−328 Indeed, Cu + disproportionates under aqueous conditions, readily giving metallic Cu 0 and Cu 2+ at RT. 329,330 These factors make assignment of the true catalytic species particularly important in the case of copper.…”

Section: Homogeneous Catalysismentioning

confidence: 99%

Electro- and Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes

et al. 2019

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The synthesis of renewable fuels from abundant water or the greenhouse gas CO 2 is a major step toward creating sustainable and scalable energy storage technologies. In the last few decades, much attention has focused on the development of nonprecious metal-based catalysts and, in more recent years, their integration in solid-state support materials and devices that operate in water. This review surveys the literature on 3d metal-based molecular catalysts and focuses on their immobilization on heterogeneous solid-state supports for electro-, photo-, and photoelectrocatalytic synthesis of fuels in aqueous media. The first sections highlight benchmark homogeneous systems using proton and CO 2 reducing 3d transition metal catalysts as well as commonly employed methods for catalyst immobilization, including a discussion of supporting materials and anchoring groups. The subsequent sections elaborate on productive associations between molecular catalysts and a wide range of substrates based on carbon, quantum dots, metal oxide surfaces, and semiconductors. The molecule–material hybrid systems are organized as “dark” cathodes, colloidal photocatalysts, and photocathodes, and their figures of merit are discussed alongside system stability and catalyst integrity. The final section extends the scope of this review to prospects and challenges in targeting catalysis beyond “classical” H 2 evolution and CO 2 reduction to C 1 products, by summarizing cases for higher-value products from N 2 reduction, C x >1 products from CO 2 utilization, and other reductive organic transformations.

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Section: Homogeneous Catalysismentioning

confidence: 99%

Electro- and Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes

et al. 2019

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“…34 Interaction of [Cu(II)] with [Ni III L 2 ] complexes in aqueous acidic condition was ruled out. 60 At lower pH the hydrogen peroxide is activated by copper(II) ion and the catalytic action of Cu(II) is due to its ready reducibility to Cu(I) as reported earlier. 61 …”

Section: Resultsmentioning

confidence: 82%

Kinetic measurements and quantum chemical calculations on low spin Ni(II)/(III) macrocyclic complexes in aqueous and sulphato medium

2015

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Cu(II) ion catalyzed kinetics of oxidation of H 2 O 2 by [Ni III L 2 ] (L 2 = 1,8-bis(2-hydroxyethyl)-1,3,6,8,10,13-hexaazacyclotetradecane) was studied in aqueous acidic medium in the presence of sulphate ion. The rate of oxidation of H 2 O 2 by [Ni III L 2 ] is faster than that by [Ni III L 1 ] (L 1 = 1,4,8,11-tetraazacyclotetradecane) in sulphate medium. DFT calculations at BP86/def2-TZVP level lead to different modes of bonding between [NiL] II/III and water ligands (L = L 1 and L 2 ). In aqueous medium, two water molecules interact with [NiL] II through weak hydrogen bonds with L and are tilted by ∼23 • from the vertical axis forming the dihydrate [NiL] 2+ .2H 2 O. However, there is coordinate bond formation between [NiL 1 ] III and two water molecules in aqueous medium and an aqua and a sulphato ligand in sulphate medium leading to the octahedral complexes [NiL 1 (H 2 O) 2 ] 3+ and [NiL 1 (SO 4 )(H 2 O)] + . In the analogous [NiL 2 ] III , the water molecules are bound by hydrogen bonds resulting in [NiL 2 ] 3+ .2H 2 O and [NiL 2 (SO 4 )] + .H 2 O. As the sulphato complex [NiL 2 (SO 4 )] + .H 2 O is less stable than [NiL 1 (SO 4 )(H 2 O)] + in view of the weak H-bonding interactions in the former it can react faster. Thus the difference in the mode of bonding between Ni(III) and the water ligand can explain the rate of oxidation of H 2 O 2 by [Ni III L] complexes.

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“…The Meerwein reaction, reaction (1), is often carried out in alkenes [14][15][16][17] though the latter are known Cu(I) ligands 19 that decrease the reduction potential of the Cu(I) ion, thus decreasing its catalytic properties. 20,21 The detailed mechanism of the Meerwein reaction is still not fully known. Some studies suggest that the first step is the formation of a π bond between the copper and the alkene forming a transient product that activates the double bond.…”

Section: Introductionmentioning

confidence: 99%

“…For comparison purposes also the kinetics of the reaction of Cu + aq and Cu I (fumarate), which is a weaker reducing agent than Cu + aq and therefore slows down many catalytic processes, 20,21 with "diazo" were studied.…”

Section: Introductionmentioning

confidence: 99%

The Cu(i) catalyzed Meerwein reaction in aqueous solutions proceeds via a radical mechanism. The effect of several ligands

et al. 2013

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The effect of the ligands 2,5,8,11-tetramethyl-2,5,8,11-tetraaza-dodecane and fumarate on the mechanism and kinetics of the Cu(I) catalyzed Meerwein reaction was studied. The results point out that initially the Cu(I) ion binds to the aromatic ring with the diazo substituent. This reaction is followed by a redox process involving N2 loss and the formation of an aryl radical, R˙. The following kinetics depends on the nature of the ligand, its effect on the redox potential and the steric hindrance it induces on the central copper ion. Clearly the ligand 2,5,8,11-tetramethyl-2,5,8,11-tetraaza-dodecane does not form an optimal catalyst with Cu(I) while it does for the Ullmann reaction.

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Ligand Effects on the Chemical Activity of Copper(I) Complexes: Outer‐ and Inner‐Sphere Oxidation of Cu^IL

Cited by 11 publications

References 55 publications

Electro- and Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes

Electro- and Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes

Kinetic measurements and quantum chemical calculations on low spin Ni(II)/(III) macrocyclic complexes in aqueous and sulphato medium

The Cu(i) catalyzed Meerwein reaction in aqueous solutions proceeds via a radical mechanism. The effect of several ligands

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Ligand Effects on the Chemical Activity of Copper(I) Complexes: Outer‐ and Inner‐Sphere Oxidation of CuIL

Cited by 11 publications

References 55 publications

Electro- and Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes

Electro- and Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes

Kinetic measurements and quantum chemical calculations on low spin Ni(II)/(III) macrocyclic complexes in aqueous and sulphato medium

The Cu(i) catalyzed Meerwein reaction in aqueous solutions proceeds via a radical mechanism. The effect of several ligands

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Ligand Effects on the Chemical Activity of Copper(I) Complexes: Outer‐ and Inner‐Sphere Oxidation of Cu^IL