Redox-photosensitized reactions. 11. Ru(bpy)32+-photosensitized reactions of 1-benzyl-1,4-dihydronicotinamide with aryl-substituted enones, derivatives of methyl cinnamate, and substituted cinnamonitriles: electron-transfer mechanism and structure-reactivity relationships

Pac, Chyongjin; Miyauchi, Yoji; Ishitani, Osamu; Ihama, Mikio; Yasuda, Masahide; Sakurai, Hiroshi

doi:10.1021/jo00175a006

Cited by 76 publications

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“…The reducing agent BNAH can potentially act either as a two-electron or one-electron donor (20)(21)(22). The two-electron process gives BNA þ via an electrochemical, chemical, and electrochemical (ECE) sequence (process 2 in Scheme 2), while the one-electron process gives 4,4′-and 4,6′-BNA 2 via the coupling The intramolecular quenching of emission from (1,1) was observed in a DMF solution without TEOA as shown in Fig.…”

Section: [1]mentioning

confidence: 99%

Photocatalytic CO ₂ reduction with high turnover frequency and selectivity of formic acid formation using Ru(II) multinuclear complexes

Tamaki

Morimoto

Koike

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

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304

238

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Previously undescribed supramolecules constructed with various ratios of two kinds of Ru(II) complexes-a photosensitizer and a catalyst-were synthesized. These complexes can photocatalyze the reduction of CO 2 to formic acid with high selectivity and durability using a wide range of wavelengths of visible light and NADH model compounds as electron donors in a mixed solution of dimethylformamide-triethanolamine. Using a higher ratio of the photosensitizer unit to the catalyst unit led to a higher yield of formic acid. In particular, of the reported photocatalysts, a trinuclear complex with two photosensitizer units and one catalyst unit photocatalyzed CO 2 reduction (Φ HCOOH ¼ 0.061, TON HCOOH ¼ 671) with the fastest reaction rate (TOF HCOOH ¼ 11.6 min −1 ). On the other hand, photocatalyses of a mixed system containing two kinds of model mononuclear Ru(II) complexes, and supramolecules with a higher ratio of the catalyst unit were much less efficient, and black oligomers and polymers were produced from the Ru complexes during photocatalytic reactions, which reduced the yield of formic acid. The photocatalytic formation of formic acid using the supramolecules described herein proceeds via two sequential processes: the photochemical reduction of the photosensitizer unit by NADH model compounds and intramolecular electron transfer to the catalyst unit. R ecently, global warming and shortages of fossil fuels and carbon resources have become serious issues. The development of technologies to convert CO 2 into useful organic compounds using sunlight as an energy source would serve as an ideal solution to these problems.Formic acid, which is the two-electron reduction product of CO 2 , has recently attracted attention as a storage source of H 2 (1, 2). Formic acid itself is an important chemical. It has been employed as a preservative and an insecticide and is also a useful acid, reducing agent, and source of carbon in synthetic chemical industries.Only a few photocatalysts for the selective formation of formic acid from CO 2 have been reported (3-8). Although oligo(p-phenylenes) (3) or a mixed system of phenazine and Co cyclam (4) successfully photocatalyzed the reduction of CO 2 to formic acid, these systems cannot work with visible light. It has been reported that ½RuðbpyÞ 2 ðCOÞ 2 2þ (bpy ¼ 2,2′-bipyridine) acted as a catalyst for reducing CO 2 (5-8). Under basic conditions, a mixed system of this complex with ½RuðbpyÞ 3 2þ as a redox photosensitizer photocatalyzed the reduction of CO 2 to formic acid with high selectivity (6, 8). However, this photocatalytic system is limited by instability as evidenced by the fact that the catalyst decomposed following prolonged irradiation and generated black precipitates.We have recently developed a unique architecture for constructing visible-light-driven supramolecular photocatalysts, consisting of a ½RuðN ∧ NÞ 3 2þ (N ∧ N ¼ a diimine ligand)-type complex as a photosensitizer and a Re(I) diimine complex as a catalyst (9-12). These supramolecules can selectively photocatalyze ...

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Section: [1]mentioning

confidence: 99%

Photocatalytic CO ₂ reduction with high turnover frequency and selectivity of formic acid formation using Ru(II) multinuclear complexes

Tamaki

Morimoto

Koike

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

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304

238

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“…All these examples provided important early evidence that various dyes can function as remarkable accelerators of some lightinduced reductions. Another type of transformations photosensitized by [Ru(bpy) 3 ] 2+ have been independently discovered by the group of Pac (Scheme 4) 19,20 . In their work, Pac et al studied reactions of various olefins with 1-benzyl-1,4-dihydronicotinamide (BNAH) as an NADH model.…”

Section: Early Examples From the 1970s To 1990smentioning

confidence: 99%

“…The reaction course was found to be governed by the structural parameters 19,20 ) of the used carbonyl compound. Thus, di-2-pyridylketone (17) led to the alcohol 18 together with a dimeric dihydronicotinamide structure 10, whereas benzaldehyde was converted to a secondary alcohol 19 in high 21,22 ) yield.…”

Section: Early Examples From the 1970s To 1990smentioning

confidence: 99%

Photoredox catalysis by [Ru(bpy)3]2+ to trigger transformations of organic molecules. Organic synthesis using visible-light photocatalysis and its 20th century roots

Teplý

2011

Collect. Czech. Chem. Commun.

462

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Reactions triggered by light constitute a treasure trove of unique synthetic methods that are available to chemists. Photoinduced redox processes using visible light in conjunction with sensitizing dyes offer a great variety of catalytic transformations useful in the realm of organic synthesis. The recent literature amply shows that this preparative toolbox is expanding substantially. This review discusses historical and contemporary work in the area of photoredox catalysis with [Ru(bpy)3]2+. Elegant examples from the most recent literature document the importance of this fast developing area of research. The photoredox chemistry has also emerged as a promising bond-making and bond-breaking tool for chemical biology and materials chemistry. A review with 96 references.

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“…[16,17] Brought to you by | New York University Bobst Library Technical Services Authenticated Download Date | 7/12/15 9:27 AM and BNAH •+ . [19,20] Brought to you by | New York University Bobst Library Technical Services Authenticated Download Date | 7/12/15 9:27 AM containing dihydropyridine moiety. Strongly reducing [Ru(bpy)3] + was proposed to transfer its electron onto the olefin substrate to generate the radical anion 13 that is then protonated to give radical intermediate 14.…”

Section: Application Of [Ru(bpy) 3 ] 2+ As Catalyst In the Twentieth mentioning

confidence: 99%

7 Visible light photoredox catalysis with [Ru(bpy)₃]²⁺: General principles and the twentieth century roots

Teplý¹

2013

Chemical Photocatalysis

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Redox-photosensitized reactions. 11. Ru(bpy)32+-photosensitized reactions of 1-benzyl-1,4-dihydronicotinamide with aryl-substituted enones, derivatives of methyl cinnamate, and substituted cinnamonitriles: electron-transfer mechanism and structure-reactivity relationships

Abstract: Die aktivierten Oiefine (I) reagieren photosettsibilisiert durch Ru‐Kontplexe mit Dihydro‐benzylnieotittattiid (H) zu den Hydrierungsproduklen (IV).

Cited by 76 publications

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Photocatalytic CO ₂ reduction with high turnover frequency and selectivity of formic acid formation using Ru(II) multinuclear complexes

Photocatalytic CO ₂ reduction with high turnover frequency and selectivity of formic acid formation using Ru(II) multinuclear complexes

Photoredox catalysis by [Ru(bpy)3]2+ to trigger transformations of organic molecules. Organic synthesis using visible-light photocatalysis and its 20th century roots

7 Visible light photoredox catalysis with [Ru(bpy)₃]²⁺: General principles and the twentieth century roots

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Redox-photosensitized reactions. 11. Ru(bpy)32+-photosensitized reactions of 1-benzyl-1,4-dihydronicotinamide with aryl-substituted enones, derivatives of methyl cinnamate, and substituted cinnamonitriles: electron-transfer mechanism and structure-reactivity relationships

Abstract: Die aktivierten Oiefine (I) reagieren photosettsibilisiert durch Ru‐Kontplexe mit Dihydro‐benzylnieotittattiid (H) zu den Hydrierungsproduklen (IV).

Cited by 76 publications

References 0 publications

Photocatalytic CO 2 reduction with high turnover frequency and selectivity of formic acid formation using Ru(II) multinuclear complexes

Photocatalytic CO 2 reduction with high turnover frequency and selectivity of formic acid formation using Ru(II) multinuclear complexes

Photoredox catalysis by [Ru(bpy)3]2+ to trigger transformations of organic molecules. Organic synthesis using visible-light photocatalysis and its 20th century roots

7 Visible light photoredox catalysis with [Ru(bpy)3]2+: General principles and the twentieth century roots

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Photocatalytic CO ₂ reduction with high turnover frequency and selectivity of formic acid formation using Ru(II) multinuclear complexes

Photocatalytic CO ₂ reduction with high turnover frequency and selectivity of formic acid formation using Ru(II) multinuclear complexes

7 Visible light photoredox catalysis with [Ru(bpy)₃]²⁺: General principles and the twentieth century roots