Atom-transfer radical reactions catalyzed by a coordinatively unsaturated diruthenium amidinate, [(η5-C5Me5)Ru(μ2-i-PrN C(Me)Ni-Pr)Ru(η5-C5Me5)]+

Motoyama, Yukihiro; Hanada, Shiori; Niibayashi, Shota; Shimamoto, Kazuya; Takaoka, Naoki; Nagashima, Hideo

doi:10.1016/j.tet.2005.08.037

Cited by 41 publications

(10 citation statements)

References 45 publications

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“…19 N ‐Allyldichloroacetamides are less reactive substrates and when standard catalysts, such as CuCl/bipy24 or [RuCl 2 (PPh 3 ) 3 ],25 are used then high reaction temperatures and/or high catalyst loadings are required. Recently, some Ru catalysts that allow the reaction to be carried out at room temperature have been described 5a,c. 24 For the cyclization of N ‐allyl‐ N ‐tosyldichloroacetamide ( 8 ), the most active Ru catalyst known to date is the methoxy‐bridged dimer [{RuCp*(OMe)} 2 ] in combination with pyridine as an activating ligand.…”

Section: Resultsmentioning

confidence: 99%

Atom‐Transfer Radical Addition (ATRA) and Cyclization (ATRC) Reactions Catalyzed by a Mixture of [RuCl₂Cp*(PPh₃)] and Magnesium

Thommes

Içli

Scopelliti

et al. 2007

Chemistry A European J

111

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A new catalytic procedure for atom-transfer radical addition (ATRA) and cyclization (ATRC) reactions is described. The combination of the ruthenium(III) complex [RuCl(2)Cp*(PPh3)] (Cp*: pentamethylcyclopentadienyl) with magnesium allows these reactions to be performed under mild conditions with high efficiency. In most cases, the catalyst concentrations required are significantly lower than those used in previously reported procedures. It is suggested that magnesium acts as a reducing agent that generates and regenerates the catalytically active ruthenium(II) species. The precatalyst [RuCl(2)Cp*(PPh3)] has been analyzed by X-ray crystallography.

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Section: Resultsmentioning

confidence: 99%

Atom‐Transfer Radical Addition (ATRA) and Cyclization (ATRC) Reactions Catalyzed by a Mixture of [RuCl₂Cp*(PPh₃)] and Magnesium

Thommes

Içli

Scopelliti

et al. 2007

Chemistry A European J

111

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“…Addition of electron‐donating groups to the indenyl ligand further increased both activity and control . Other systems using nitrogen‐ or oxygen‐based ligands have also been explored . ICAR initiation system was also successfully extended to Ru‐based ATRP …”

Section: Ru‐ and Fe‐based Atrp Catalystsmentioning

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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“…Recently, some bimetallic [19] and amidinato [20] complexes have also been described as efficient catalyst for the polymerization of styrene and various acrylates.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and structural chemistry of bis(pyridylimino)isoindolato–ruthenium complexes and their activity as mediators in the atom transfer radical polymerization (ATRP) of styrene

Camerano

Rodrigues²,

Röminger

et al. 2011

Journal of Organometallic Chemistry

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Atom-transfer radical reactions catalyzed by a coordinatively unsaturated diruthenium amidinate, [(η5-C5Me5)Ru(μ2-i-PrN C(Me)Ni-Pr)Ru(η5-C5Me5)]+

Cited by 41 publications

References 45 publications

Atom‐Transfer Radical Addition (ATRA) and Cyclization (ATRC) Reactions Catalyzed by a Mixture of [RuCl₂Cp*(PPh₃)] and Magnesium

Atom‐Transfer Radical Addition (ATRA) and Cyclization (ATRC) Reactions Catalyzed by a Mixture of [RuCl₂Cp*(PPh₃)] and Magnesium

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

Synthesis and structural chemistry of bis(pyridylimino)isoindolato–ruthenium complexes and their activity as mediators in the atom transfer radical polymerization (ATRP) of styrene

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Atom-transfer radical reactions catalyzed by a coordinatively unsaturated diruthenium amidinate, [(η5-C5Me5)Ru(μ2-i-PrN C(Me)Ni-Pr)Ru(η5-C5Me5)]+

Cited by 41 publications

References 45 publications

Atom‐Transfer Radical Addition (ATRA) and Cyclization (ATRC) Reactions Catalyzed by a Mixture of [RuCl2Cp*(PPh3)] and Magnesium

Atom‐Transfer Radical Addition (ATRA) and Cyclization (ATRC) Reactions Catalyzed by a Mixture of [RuCl2Cp*(PPh3)] and Magnesium

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

Synthesis and structural chemistry of bis(pyridylimino)isoindolato–ruthenium complexes and their activity as mediators in the atom transfer radical polymerization (ATRP) of styrene

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Product

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Atom‐Transfer Radical Addition (ATRA) and Cyclization (ATRC) Reactions Catalyzed by a Mixture of [RuCl₂Cp*(PPh₃)] and Magnesium

Atom‐Transfer Radical Addition (ATRA) and Cyclization (ATRC) Reactions Catalyzed by a Mixture of [RuCl₂Cp*(PPh₃)] and Magnesium