Redox-coupled structural changes in copper chemistry: Implications for atom transfer catalysis

Zerk, Timothy J.; Bernhardt, Paul V.

doi:10.1016/j.ccr.2017.11.016

Cited by 34 publications

(36 citation statements)

References 146 publications

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“…This reaction is referred to as the equilibrium of organometallic‐mediated polymerization (OMRP) . For copper with secondary acrylate or cyanoalkyl radicals, the OMRP equilibrium is strongly shifted to the right ( K OMRP ≈ 10 8 ) . However, the concentration of the OMRP dormant species, P n ‐Cu II L + , is typically low in ATRP due to both low [R • ] and low [Cu I L + ].…”

Section: Mechanistic Aspects Of Atrpmentioning

confidence: 99%

“…However, the concentration of the OMRP dormant species, P n ‐Cu II L + , is typically low in ATRP due to both low [R • ] and low [Cu I L + ]. The formation of P n ‐Cu II L + is fast, with k add ≈ 10 4 –10 5 m −1 s −1 at −40 °C, and k add ≈ 10 7 m −1 s −1 at room temperature . Consequently, dissociation is relatively slow, k dis ≈ 10 −1 s −1 .…”

Section: Mechanistic Aspects Of Atrpmentioning

confidence: 99%

“…Further studies proved that it is formally a 4‐coordinate distorted tetrahedral complex, due to the Cu I ‐N ax bond length of 2.411 Å, which can be considered nonbonding . The deactivator complex adopts an almost perfect trigonal bipyramidal geometry, with the Cu II cation coordinated by all four nitrogen atoms of the TPMA ligand, and a Br anion coordinated in the axial position . Deactivation is efficient because there is minimal rearrangement in the conversion between Cu I and Cu II centers …”

Section: Development Of Ligands For More Active and Selective Atrp Camentioning

confidence: 99%

See 2 more Smart Citations

Atom Transfer Radical Polymerization: Billion Times More Active Catalysts and New Initiation Systems

Ribelli

Lorandi

Fantin

et al. 2018

Macromol. Rapid Commun.

235

184

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polymerizing styrene in the presence of 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) radicals. [10] Later, Wayland et al. used a cobalt(II) porphyrin complex to reversibly trap radical species during the polymerization of acrylate monomers, which showed living features: i) linear increase of polymer MW with monomer conversion, and ii) narrow MWD. [11] These techniques set the basis for the development of nitroxide-mediated polymerization (NMP) [12,13] and organometallic mediated radical polymerization (OMRP). [14][15][16] Within the past three decades, controlled radical polymerization (CRP) has been established as a new field in polymer chemistry, in which exceptional control was achieved over polymer architectures, thus enabling the preparation of commercially relevant polymer-based materials for advanced applications. Following IUPAC recommendations, CRP should be termed as reversible deactivation radical polymerization (RDRP). [17] Besides the aforementioned NMP and OMRP, the most affirmed RDRPs are atom transfer radical polymerization (ATRP) [18][19][20] and reversible additionfragmentation chain transfer (RAFT) polymerization. [21] RDRP ensures comparable degree of control as living ionic polymerization, while retaining the versatility and the scope of conventional radical polymerization. The fraction of terminated chains in RDRP is small, typically below a few mol%. Polymers and copolymers prepared by RDRP methods can have defined topologies (stars, brushes, networks, combs), compositions (block, gradient, graft, alternate) and chain-end functionalities. [22] This review will focus on ATRP, with particular attention to the design and application of progressively more active and selective copper-based catalysts, and the development of novel, more benign initiation systems. The correlation between the structure of Cu complexes and their catalytic activity will be discussed in detail, also taking into account the effect of solvent and, when present, surfactants and other additives. Mechanisms of Reversible Deactivation Radical Polymerization ProcessesThe core of all RDRP systems is the increase of chain lifetime by reversibly deactivating the propagating radical species, thus forming dormant species that can be subsequently reactivated. As opposed to conventional RP in which the 25 Years of ATRP Approaching 25 years since its invention, atom transfer radical polymerization (ATRP) is established as a powerful technique to prepare precisely defined polymeric materials. This perspective focuses on the relation between structure and activity of ATRP catalysts, and the consequent choice of the initiating system, which are paramount aspects to well-controlled polymerizations. The ATRP mechanism is discussed, including the effect of kinetic and thermodynamic parameters and side reactions affecting the catalyst. The coordination chemistry and activity of copper complexes used in ATRP are reviewed in chronological order, while emphasizing the structure-activity correlation. ATRP-initiating systems are described, from ...

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Section: Mechanistic Aspects Of Atrpmentioning

confidence: 99%

Section: Mechanistic Aspects Of Atrpmentioning

confidence: 99%

Section: Development Of Ligands For More Active and Selective Atrp Camentioning

confidence: 99%

See 1 more Smart Citation

Atom Transfer Radical Polymerization: Billion Times More Active Catalysts and New Initiation Systems

Ribelli

Lorandi

Fantin

et al. 2018

Macromol. Rapid Commun.

235

184

View full text Add to dashboard Cite

show abstract

“…Complexes of various transition metal ions have been used in ATRP including those of groups 5 (V), 4, 5 6 (Mo), [6][7][8] 7 (Mn), 9 8 (Fe & Ru), [10][11][12][13][14][15][16] 9 (Co) 17 and 10 (Ni) 18 , but the vast majority of studies (~ 65%) utilise Cu. 19,20 [Cu Multidentate, N-donor ligands (L) are typically used to solubilise the copper ion and concomitantly tune the position of the central equilibrium constant (KATRP) by controlling the thermodynamic and kinetic properties of the transition metal complex. 19,21,22 One of the most popular ligands in this regard is tris-(2-dimethylaminoethyl)amine (Me6tren) which chelates the cuprous ion as a tripodal, N4-donor occupying all four possible coordination sites (i.e.…”

Section: Introductionmentioning

confidence: 99%

“…19,20 [Cu Multidentate, N-donor ligands (L) are typically used to solubilise the copper ion and concomitantly tune the position of the central equilibrium constant (KATRP) by controlling the thermodynamic and kinetic properties of the transition metal complex. 19,21,22 One of the most popular ligands in this regard is tris-(2-dimethylaminoethyl)amine (Me6tren) which chelates the cuprous ion as a tripodal, N4-donor occupying all four possible coordination sites (i.e. no additional ligands are coordinated) to form the active catalyst [Cu I (Me6tren)] + .…”

Section: Introductionmentioning

confidence: 99%

The fate of copper catalysts in atom transfer radical chemistry

et al. 2019

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Unlocking the Potential of Redox‐Active Copper Complexes in Thin Films via Proton‐Coupled Electron Transfer for Enhanced Supercapacitor Performance

Gupta,

Malik,

Sachan

et al. 2024

Adv Funct Materials

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Nanoscale redox‐active molecular films are promising candidates for next‐generation energy storage applications due to their ability to facilitate long‐range charge transport. However, establishing stable and efficient electrode‐molecule interfaces remains a critical challenge. In this study, the properties of redox‐active copper‐polypyridyl thin films covalently bonded to graphite rods are explored, investigating their potential as supercapacitors. Using an electrochemical grafting method, robust covalent interfaces are created, resulting in copper‐polypyridyl films prepared on graphite rods and indium tin oxide (ITO) electrodes, exhibiting both Cu(II) and Cu(I) redox states. These redox‐active mettalo‐oligomeric films demonstrate a structural transition between octahedral and tetrahedral geometries around the Cu(II), and Cu(I), respectively contributing to their charge storage capabilities. The combination of an electrical double‐layer capacitance and pseudocapacitance through Faradaic charge transfer is evaluated in different acidic electrolytes, showing significant capacitance enhancement. Notably, proton‐coupled electron transfer (PCET) at free pyridine‐N sites in Cu(I) polypyridyl complex is identified as a key factor in their distinct behavior in aqueous solutions, a finding supported by computational studies. This study shows the potential of binder‐free thin films for efficient supercapacitor applications, with a maximum areal capacitance of 6.8 mF cm⁻2 in aqueous media, representing an 1840% improvement over bare graphite rods.

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Redox-coupled structural changes in copper chemistry: Implications for atom transfer catalysis

Cited by 34 publications

References 146 publications

Atom Transfer Radical Polymerization: Billion Times More Active Catalysts and New Initiation Systems

Atom Transfer Radical Polymerization: Billion Times More Active Catalysts and New Initiation Systems

The fate of copper catalysts in atom transfer radical chemistry

Unlocking the Potential of Redox‐Active Copper Complexes in Thin Films via Proton‐Coupled Electron Transfer for Enhanced Supercapacitor Performance

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