Dataset Information

Improved Conditions for the Visible-Light Driven Hydrocarboxylation by Rh(I) and Photoredox Dual Catalysts Based on the Mechanistic Analyses.

ABSTRACT: The improved catalytic conditions and detailed reaction mechanism of the visible-light driven hydrocarboxylation of alkenes with CO₂ by the Rh(I) and photoredox dual catalysts were investigated. The use of the benzimidazoline derivative, BI(OH)H, as a sacrificial electron donor was found to increase the yield of the hydrocarboxylated product by accelerating the reduction process. In addition, the incorporation of the cyclometalated Ir(III) complex as a second photosensitizer with [Ru(bpy)₃]²⁺ photosensitizer also resulted in the promotion of the reduction process, supporting that the catalytic cycle includes two photochemical elementary processes: photoinduced electron and energy transfers.

SUBMITTER: Murata K

PROVIDER: S-EPMC6558419 | biostudies-literature | 2019

REPOSITORIES: biostudies-literature

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Publications

Improved Conditions for the Visible-Light Driven Hydrocarboxylation by Rh(I) and Photoredox Dual Catalysts Based on the Mechanistic Analyses.

Murata Kei K Numasawa Nobutsugu N Shimomaki Katsuya K Takaya Jun J Iwasawa Nobuharu N

Frontiers in chemistry 20190522

The improved catalytic conditions and detailed reaction mechanism of the visible-light driven hydrocarboxylation of alkenes with CO<sub>2</sub> by the Rh(I) and photoredox dual catalysts were investigated. The use of the benzimidazoline derivative, BI(OH)H, as a sacrificial electron donor was found to increase the yield of the hydrocarboxylated product by accelerating the reduction process. In addition, the incorporation of the cyclometalated Ir(III) complex as a second photosensitizer with [Ru( ...[more]

PMID: 31231630

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Project description:A ruthenium aqua photoredox catalyst has been successfully heterogeneneized on graphene oxide (GO@trans-fac-3) and graphite rods (GR@trans-fac-3) for the first time and have proven to be sustainable and easily reusable systems for the photooxidation of alcohols in water, in mild and green conditions. We report here the synthesis and total characterization of two Ru(II)-polypyridyl complexes, the chlorido trans-fac-[RuCl(bpea-pyrene)(bpy)](PF6) (trans-fac-2) and the aqua trans-fac-[Ru(bpea-pyrene)(bpy)OH2](PF6)2 (trans-fac-3), both containing the N-tridentate, 1-[bis(pyridine-2-ylmethyl)amino]methylpyrene (bpea-pyrene), and 2,2'-bipyridine (bpy) ligands. In both complexes, only a single isomer, the trans-fac, has been detected in solution and in the solid state. The aqua complex trans-fac-3 displays bielectronic redox processes in water, assigned to the Ru(IV/II) couple. The trans-fac-3 complex has been heterogenized on different types of supports, (i) on graphene oxide (GO) through π-stacking interactions between the pyrene group of the bpea-pyrene ligand and the GO and (ii) both on glassy carbon electrodes (GC) and on graphite rods (GR) through oxidative electropolymerization of the pyrene group, which yield stable heterogeneous photoredox catalysts. GO@trans-fac-3- and GR/poly trans-fac-3-modified electrodes were fully characterized by spectroscopic and electrochemical methods. Trans-fac-3 and GO@trans-fac-3 photocatalysts (without a photosensitizer) showed good catalytic efficiency in the photooxidation of alcohols in water under mild conditions and using visible light. Both photocatalysts display high selectivity values (>99%) even for primary alcohols in accordance with the presence of two-electron transfer processes (2e-/2H+). GO@trans-fac-3 keeps intact its homogeneous catalytic properties but shows an enhancement in yields. GO@trans-fac-3 can be easily recycled by filtration and reused for up to five runs without any significant loss of catalytic activity. Graphite rods (GR@trans-fac-3) were also evaluated as heterogeneous photoredox catalysts showing high turnover numbers (TON) and selectivity values.

Dataset Information

Improved Conditions for the Visible-Light Driven Hydrocarboxylation by Rh(I) and Photoredox Dual Catalysts Based on the Mechanistic Analyses.

Publications

Improved Conditions for the Visible-Light Driven Hydrocarboxylation by Rh(I) and Photoredox Dual Catalysts Based on the Mechanistic Analyses.

Similar Datasets

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