Syntheses, Structures and Properties of Copper(I) and Copper(II) Complexes of the LigandN,N′-Bis[2′-(dimethylamino)ethyl]-N,N′-dimethylethane1,2-diamine (Me6trien)

Becker, Matthias; Heinemann, Frank W.; Knoch, Falk; Donaubauer, Wolfgang; Liehr, Günter; Schindler, Siegfried; Golub, Gilad; Cohen, Haim; Meyerstein, Dan

doi:10.1002/(sici)1099-0682(200004)2000:4<719::aid-ejic719>3.0.co;2-n

Cited by 31 publications

(26 citation statements)

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“…Structural studies of Cu I ClO 4 chelated by Me 6 TREN showed that the Cu I cation is coordinated by four nitrogen atoms, with the bond between Cu and the axial nitrogen atom being slightly longer (Cu I ‐N ax = 2.200 Å) than the equatorial bonds (Cu I ‐N eq = 2.122 Å), as displayed in Figure . The geometry is best described as distorted trigonal bipyramidal because of the weak interaction with the perchlorate anion (omitted for clarity), although in solution the anion is likely completely dissociated . In solution this species is in equilibrium with the neutral species Br‐Cu I (Me 6 TREN), as well as with a species in which one arm of the ligand is dissociated from the Cu I center .…”

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

confidence: 99%

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: Development Of Ligands For More Active and Selective Atrp Camentioning

confidence: 99%

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

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“…When the dinuclear copper(I) complex of this ligand was reacted with dioxygen, an extremely stable peroxo complex was formed. [48] Scheme 7. [71] When three linkers are used to connect two tren units, cryptands are obtained.…”

Section: Bridging Ligands Derived From Tren and Derivativesmentioning

confidence: 87%

“…Theoretical calculations were also employed in the design of this ligand. [48] Crystal structures show the two compounds to be isostructural. A typical example is L 14 , shown in Scheme 6.…”

Section: Bridging Ligands Derived From Tren and Derivativesmentioning

confidence: 87%

“…The potential of this approach has been highlighted by Bol et al, who synthesized the macrocyclic ligand MEPY22PZ (Scheme 6). [48] The copper(I) complex of Me 6 trien {N,NЈ-bis[2Ј-(dimethylamino)ethyl]-N,NЈ-dimethylethane-1,2-diamine; Scheme 7}, an isomer of Me 6 tren, can be synthesized by a comproportionation reaction in water. When the dinuclear copper(I) complex of this ligand was reacted with dioxygen, an extremely stable peroxo complex was formed.…”

Section: Bridging Ligands Derived From Tren and Derivativesmentioning

confidence: 99%

“…[31,118,119] The above results are corroborated by investigations on tridentate ligands carried out in this laboratory. [48,50] Timeresolved spectra of the reaction of copper(I) Me 5 dien with dioxygen at Ϫ90°C are shown in Figure 4. [122,123] Me 5 dien can be regarded as Me 6 trien or Me 6 tren with one arm missing.…”

Section: Bridging Ligands Derived From Tren and Derivativesmentioning

confidence: 99%

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