Highly selective photo-catalytic dimerization of α-methylstyrene by a novel palladium complex with photosensitizing ruthenium(ii) polypyridyl moiety

Inagaki, Akiko; Edure, Shinichi; Yatsuda, Shinichi; Akita, Munetaka

doi:10.1039/b508013d

Cited by 55 publications

(26 citation statements)

References 25 publications

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“…Dimerisation of 1-olefins. The heterobinuclear complex 1 (Scheme 1), recently reported by Akita et al 10 serves as a precatalyst for the photocatalytic dimerisation of 1-methylstyrene. Mechanistic investigations (scheme 2) suggest that the catalytic cycle starts with the palladium-hydrido species, B. Insertion of 1-methyl-styrene into the Pd-H bond then yields the complex C, which has been isolated and characterised.…”

Section: (A) Photocatalytic Reactions Based On Energy Transfermentioning

confidence: 99%

Inspired by nature: light driven organometallic catalysis by heterooligonuclear Ru(ii) complexes

2007

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In view of diminishing resources and an ever increasing demand for energy attention has been directed towards the development of new photocatalytic systems modelling natural photosynthesis. Recent investigations have shown that supramolecular devices consisting of photosynthetic reaction centres and catalyst metals--connected via bridging ligands--are capable of performing light driven catalytic reactions such as hydrogen production, reduction of CO(2), and conversion reactions of olefins.

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Section: (A) Photocatalytic Reactions Based On Energy Transfermentioning

confidence: 99%

Inspired by nature: light driven organometallic catalysis by heterooligonuclear Ru(ii) complexes

2007

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“…[4,[10][11][12][13] The majority of the reported dual catalytic systems feature individual catalysts added separately to the reaction mixture, however there is a growing interest in developing single compounds that feature two distinct catalytic sites. [14] Chemically tethering different types of catalysts could allow increased cooperation between the catalytic centres, [15][16][17] potentially leading to new reactivity being discovered. It is particularly advantageous to utilise this tethering strategy in photocatalysis, Figure 1.…”

Section: Introductionmentioning

confidence: 99%

Understanding the Synergistic Effects Observed When Using Tethered Dual Catalysts for Heat and Light Activated Catalysis

et al. 2020

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Dual catalysis, where two different catalysts work cooperatively to promote a chemical reaction, is an important synthetic approach as it can allow a wide range of unique reactivity to be accessed. Whilst most dual catalysis strategies utilise separate catalysts in the reaction mixture, there is a growing interest in using tethered dual catalysts to increase cooperativity between the catalytic centres. In this current work we sought to determine the origin of the catalytic synergy observed for a series of Ir(I) based complexes tethered to a BODIPY type photocatalyst through different tethering modes. Kinetic analyses revealed that the tethered dual catalysts were more effective at promoting heat activated intermolecular hydro-amination than the un-tethered analogues. The tethering mode had a significant influence on the magnitude of this synergistic enhancement observed for the hydroamination reaction, likely due to a combination of steric and electronic ligand effects. Investigations into the effect of the tethered dual catalysts on the light activated oxidation of thioanisole demonstrated that chemical tethering leads to substantial increases in photocatalytic activity, which was once again impacted by the tethering mode. The origin of the observed enhancement was found to be due to both increased singlet oxygen generation through the heavy atom effect, as well as direct involvement of the Ir centre in the oxidation reaction pathway.

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“…4-methyl-4′-[2-(2-naphthyl)ethyl]-2,2′-bipyridine (bpy C2H4naph ), 9f 2,2′-bipyrimidine (bpm), 26 5,5′-dibromo-2,2′bipyrimidine (bpm Br ), 25 4-bromo-2,2′-bipyridyl, 27 2-naphthylboronic acid 28 were prepared according to the published methods. The metal reagents, [Pd(cod)MeCl], 29 and other metal complexes [(bpy H ) 2 Ru(bpm H )](BF 4 ) 2 , 6 [(bpy H ) 2 Ru-(bpm Br )](BF 4 ) 2 , 6 and [(bpy H ) 2 Ru(bpm Br )Pd(Me)(Me 2 CO)](BF 4 ) 3 , 6[(bpy naph ) 2 Ru(bpm Br )](BF 4 ) 2 (1), 10a and [(bpy naph ) 2 Ru(bpm Br )-Pd(Me)(Me 2 CO)](BF 4 ) 3 (1-Pd) 10a were prepared according to the published procedures. Other chemicals were purchased and used as received.…”

Section: Generalmentioning

confidence: 99%

“…The introduction of a Pd unit as a reaction center was accomplished using previously established methods. 6,7,11 In this paper, we describe the synthesis of such bichromophoric Pd catalysts bearing naphthyl and Ru(II)-polypyridyl units as UV and visible light sensitive chromophores, respectively. Their photophysical and electrochemical properties and their catalytic activity toward styrene are also presented.…”

Section: Introductionmentioning

confidence: 99%

Syntheses, photophysical properties, and reactivities of novel bichromophoric Pd complexes composed of Ru(ii)–polypyridyl and naphthyl moieties

Murata¹,

Araki²,

Inagaki³

et al. 2013

Dalton Trans.

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A series of novel bichromophoric Ru(II) complexes bearing a naphthyl chromophore linked with 2,2'-bipyridyl (bpy) and 2,2'-bipyrimidine (bpm) ligands were synthesized. Complexation with a Pd-alkyl unit led to the formation of bichromophoric Ru-Pd catalysts. The photochemical and electrochemical properties of the newly synthesized compounds were studied. It has been shown that the UV-light energy absorbed at the pendant naphthyl moiety is effectively transferred to the Ru(II) center; this is supported by the observation of metal-to-ligand charge-transfer luminescence through excitation of the naphthyl unit, which is identical to the luminescence observed through visible light excitation. The luminescence lifetime of the complex bearing a naphthyl moiety directly connected to the bpy ligands was lengthened to ca. 1000 ns. When a Pd complex containing the bichromophoric unit with an extended lifetime was used as a catalyst, styrene polymerization under visible or UV light irradiation was observed, in clear contrast to dimerization using other catalysts. These results indicate the formation of an excited-state with a prolonged excited-state lifetime, which promotes an insertion step in preference to the competing β-H elimination step.

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Highly selective photo-catalytic dimerization of α-methylstyrene by a novel palladium complex with photosensitizing ruthenium(ii) polypyridyl moiety

Abstract: A novel dinuclear complex containing the photo-sensitizing Ru unit and a Pd center is effective toward selective catalytic dimerization of alpha-methylstyrene leading to 2,4-diphenyl-4-methyl-1-pentene under visible-light irradiated conditions.

Cited by 55 publications

References 25 publications

Inspired by nature: light driven organometallic catalysis by heterooligonuclear Ru(ii) complexes

Inspired by nature: light driven organometallic catalysis by heterooligonuclear Ru(ii) complexes

Understanding the Synergistic Effects Observed When Using Tethered Dual Catalysts for Heat and Light Activated Catalysis

Syntheses, photophysical properties, and reactivities of novel bichromophoric Pd complexes composed of Ru(ii)–polypyridyl and naphthyl moieties

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