- Arylruthenium(III) Porphyrin-Catalyzed C-H Oxidation and Epoxidation at Room Temperature and [RuV(Por)(O)(Ph)] Intermediate by Spectroscopic Analysis and Density Functional Theory Calculations
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The development of highly active and selective metal catalysts for efficient oxidation of hydrocarbons and identification of the reactive intermediates in the oxidation catalysis are long-standing challenges. In the rapid hydrocarbon oxidation catalyzed by ruthenium(IV) and -(III) porphyrins, the putative Ru(V)-oxo intermediates remain elusive. Herein we report that arylruthenium(III) porphyrins are highly active catalysts for hydrocarbon oxidation. Using catalyst [RuIII(TDCPP)(Ph)(OEt2)] (H2TDCPP = 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin), the oxidation of C-H bonds of various hydrocarbons with oxidant m-CPBA at room temperature gave alcohols/ketones in up to 99% yield within 1 h; use of [nBu4N]IO4 as a mild alternative oxidant avoided formation of lactone from cyclic ketone in C-H oxidation, and the catalytic epoxidation with up to 99% yield and high selectivity (no aldehydes as side product) was accomplished within 5 min. UV-vis, electrospray ionization-mass spectrometry, resonance Raman, electron paramagnetic resonance, and kinetic measurements and density functional theory calculations lend evidence for the formation of Ru(V)-oxo intermediate [RuV(TDCPP)(O)(Ph)].
- Shing, Ka-Pan,Cao, Bei,Liu, Yungen,Lee, Hung Kay,Li, Ming-De,Phillips, David Lee,Chang, Xiao-Yong,Che, Chi-Ming
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supporting information
p. 7032 - 7042
(2018/06/12)
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- Sandwich structure of a ruthenium porphyrin and an amino acid hydrazide for probing molecular chirality by circular dichroism
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Owing to the strong Lewis acidity of ruthenium porphyrins, a commercial carbonyl ruthenium porphyrin and an amino acid hydrazide can assemble into a sandwich structure. The nature of such a structure is diagnostic of the absolute configuration of the amino acid by circular dichroism.
- Liang, Qing-Feng,Liu, Juan-Juan,Chen, Jian
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supporting information; experimental part
p. 3987 - 3991
(2011/08/09)
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- A mild catalytic oxidation system: Ruthenium porphyrin and 2,6-dichloropyridine n-oxide applied for alkene dihydroxylation
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A new method was developed to transform alkenes into three types of functional molecules, including epoxides, aldehydes and 1,2-diols by using dichlororuthenium(IV) meso-tetrakis(2,6-dichlorophenyl)porphyrin [Ru(IV)(TDCPP)Cl2] as catalyst and 2,6-dichloropyridine N-oxide (Cl2pyNO) as the oxidant, in which the 1,2-diols were afforded via "one-pot" reactions in moderate yields. Copyright
- Hu, Wen-Xiang,Li, Pei-Rong,Jiang, Gaoxi,Che, Chi-Ming,Chen, Jian
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experimental part
p. 3190 - 3194
(2011/02/23)
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- Preparation and crystal structure of trans-dihydroxo-[tetrakis(2,6-dichlorophenyl)porphinato]ruthenium(IV).2toluene
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Trans-dihydroxo-[tetrakis(2,6-dichlorophenyl)porphinato]ruthenium(IV), ([Ru(OH)2(TDCPP)]) was prepared by meta-chloroperbenzoic acid oxidation of [Ru(CO)(TDCPP)] in dichloromethane-toluene, and its crystal structureis reported. Crystal data for [Ru(OH)2(TDCPP)].2toluene: C44H22N4O2Cl8Ru.2C7H8, orthorhombic, space group Pbca, a=13.149(1), b=19.893(2), c=21.093(2) ?, U=5517.3(2) ?**3, Z=4. The short axial Ru-O bond distance, 1.790(7) ?, is in the range expected for a double Ru(IV)-oxygenbond. Both hydroxo ligands are approximately located in the mean plane of two opposite dichlorophenyl groups. Full-matrix least-squares refinement of positional and thermal parameters, using 2368 unique reflections with F>2.5σ(F) led to R(F)=0.063; R(w)=0.066.
- Dubourdeaux, Patrick,Tavares, Manuella,Grand, Andre,Ramasseul, Rene,Marchon, Jean-Claude
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p. 657 - 660
(2008/10/08)
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