Mechanistic investigations of the photosensitized reactions of iron arene complexes

Karatsu, Takashi; Shibuki, Yukio; Miyagawa, Nobukazu; Takahara, Shiro; Kitamura, Akihiro; Yamaoka, Tsuguo

doi:10.1016/s1010-6030(96)04578-9

Cited by 20 publications

(20 citation statements)

References 11 publications

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“…Among ferroceniums, Irgacure 261 i.e. (η 6 -(1-methylethyl)phenyl)(η 5 -cyclopentadienyl)iron hexafluorophosphate is a popular photoinitiator of cationic polymerization as this compound is commercially available [158][159][160][161][162][163][164]. However, the maximum absorption is centered at 241 nm and the absorption of Irgacure 261 extends from 200 to 300 nm so that this ferrocenium salt is a UV-centered photoinitiator.…”

Section: Carbazole-based Ferroceniummentioning

confidence: 99%

Recent advances on carbazole-based photoinitiators of polymerization

Dumur

2020

European Polymer Journal

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Photoinitiators of polymerization that can be activated under visible light and low intensity are actively researched as these compounds constitute the next generation of photoinitiators that will replace the controverted UV-photoinitiators. Over the years, a family of compounds has been identified as being highly promising in light of its remarkable photoinitiating ability, photochemical stability, low cost and easiness to functionalize, namely carbazoles. In this review, an overview of the different carbazole-based photoinitiators reported to date is presented. Interestingly, carbazoles have mostly been used as electron donors in push-pull structures, as photosensitizers for iodonium salts, as ligands for ferrocenium salts or as chromophores for phenacyl onium salts. These different applications clearly demonstrate the versatility of this structure used as the elemental building block for the design of UV, near-UV or visible light photoinitiators.

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Section: Carbazole-based Ferroceniummentioning

confidence: 99%

Recent advances on carbazole-based photoinitiators of polymerization

Dumur

2020

European Polymer Journal

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“…But its reactivity was more generally investigated for its applications in Organic Chemistry. [84] Upon excitation in the UV range, Irgacure 261 can be used as a single component capable to initiate the polymerization process. Notably, the cationic ring-opening polymerization of ((9-carbazolyl)methyl)thiirane (CMT) and ((10-phenothiazinyl)methyl) thiirane (PMT) was investigated with Irgacure 261 and for comparison, different photoinitiators such as iodonium or sulfonium salts were tested (See Figure 2).…”

Section: Ferrocenium Salts Used As Photoinitiators Of Polymerization mentioning

confidence: 99%

Recent advances on iron-based photoinitiators of polymerization

Dumur

2020

European Polymer Journal

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With regards to the environmental and safety concerns raised nowadays by the polymer industry, polymerization processes requiring light as the activation source are currently knowing a revival of interest after decades of disinterest. Recent progresses in photopolymerization are notably sustained by the development of new polymerization application namely 3D and 4D printing enabling an unprecedented access to structures of incredible complexity. Parallel to the manufacturing process, the polymer material itself and its composition are also facing numerous questions concerning their environmental and human health impacts. Beyond the monomers, the different additives introduced in the resin can also be potentially toxic so that a great deal of efforts is currently done to develop new photoinitiators with a toxicity assessed as being insignificant. In this field, iron-based metal complexes are candidates of choice due to the clinical demonstration of their very low toxicities. Among iron complexes, ferrocene is among the most widely studied iron-based metallocene. Due to its unique and reversible electrochemical properties as well as their absorption centred in the visible range, numerous photoinitiators have been developed with ferrocene or its oxidized form i.e. ferrocenium. Parallel to this, the remarkable electrochemical properties of ferrocenium made it an excellent candidate for its incorporation in photoinitiating systems. However, interest for iron-based photoinitiators was not limited to ferrocene and ferrocenium, and Schiff base complexes were also successfully used as initiators of polymerization. In this review, an overview of the different iron-based photoinitiating systems reported to date is presented. More precisely, if iron-based photoinitiators are developed since 50 years, a special focus will be done on photoinitiators designed for recent polymerization conditions, namely, under visible light and low light intensity.

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“…In the absence of appropriate ligands, the initially formed [(C 5 R 5 )Fe] + species undergo further decomposition to give Fe 2+ ions, which can be used for photocatalytic polymerization of epoxides [25,26] and cyanates, [27] as well as for photoprinting by coordination with salicylate organic dyes [28,29] (interestingly some ferrocene derivatives can be also used in a similar way) [30,31] . Despite a variety of these applications, the fate of cyclopentadienyl ligand in the photochemical decomposition of [(C 5 R 5 )Fe(arene)] + has remained unclear before this study (the formation of ferrocene as a by‐product has been noted in aprotic solvents such as THF) [13,32] . In somewhat related work, cyclopentadienol has been generated by the non‐photochemical decomposition of ferrocenium cation in air [33] …”

Section: Introductionmentioning

confidence: 96%

“…Cyclopentadienyl iron complexes with arene ligands [(C 5 R 5 )Fe(arene)] + are air‐stable compounds which can be readily obtained from ferrocenes in one step ( Scheme 2). [11] Under irradiation with visible light, they undergo decomposition giving [(C 5 R 5 )Fe] + species and free arenes [12–15] . This ability has been used in organic synthesis for modification and further liberation of the arene ligands.…”

Section: Introductionmentioning

confidence: 99%

“…[11] Under irradiation with visible light, they undergo decomposition giving [(C 5 R 5 )Fe] + species and free arenes. [12][13][14][15] This ability has been used in organic synthesis for modification and further libera-tion of the arene ligands. In particular, polycyclic arenes, [16,17] cyclophanes, [18] dendrimers, [19] and polymers [20] have been synthesized this way.…”

Section: Introductionmentioning

confidence: 99%

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Generation of Cyclopentadiene for Diels–Alder Reactions by Visible‐Light Irradiation of Iron Sandwich Complexes

Sokolov

Polezhaev

Nelyubina

et al. 2022

Helvetica Chimica Acta

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Cyclopentadienes readily undergo fast and selective Diels-Alder reactions which can be used for conjugation of biomolecules and polymers. Herein we present a new method for the photochemical generation of cyclopentadienes by the visible light irradiation of the iron complexes [(C 5 H 4 R)Fe(arene)] + . This reaction proceeds at room temperature, in water, and in the presence of potentially interfering amino acids. Free cyclopentadiene is trapped by dienophiles to give the corresponding Diels-Alder adducts in 72-95 % yield.

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Mechanistic investigations of the photosensitized reactions of iron arene complexes

Cited by 20 publications

References 11 publications

Recent advances on carbazole-based photoinitiators of polymerization

Recent advances on carbazole-based photoinitiators of polymerization

Recent advances on iron-based photoinitiators of polymerization

Generation of Cyclopentadiene for Diels–Alder Reactions by Visible‐Light Irradiation of Iron Sandwich Complexes

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