Ruthenium and Osmium: High Oxidation States

Che, Chi‐Ming; Lau, Tai‐Chu

doi:10.1016/b0-08-043748-6/04215-8

Cited by 18 publications

(16 citation statements)

References 558 publications

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“…The result is not surprising, as NR can be considered as isoloble with O and it is well-known that nitrogen-containing and oxo ligands can stabilize Ru metal centers with high oxidation states. 26 On the basis of the electrocyclization mechanism via C1 (Scheme 1), we do not expect that 9 f 10 occurs (Scheme 3). Indeed, product 10 was not produced or produced in only a trace amount, after 9 was heated at 80°C in DME in the presence of 2 mol % RuCl 3 for 24 h. Introduction of a CH 2 moiety eliminates the possibility of having an electrocyclization mechanism because the two phenyl rings in 9 are not in conjugation with each other.…”

Section: Articlementioning

confidence: 97%

Ruthenium-Catalyzed Intramolecular Amination Reactions of Aryl- and Vinylazides

et al. 2009

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The catalytic activity of a series of ruthenium complexes for C-H amination reactions of organic azides was investigated. The most active catalyst was found to be RuCl 3 , which promotes C-H amination reactions of ortho-aryl phenylazides, 1-azido-2-arylvinylazides, and 1-azido-1,3-butadienes to give carbazoles, indoles, and pyrroles, respectively. Both computational and experimental results support that a two-step process involving formal electrocyclization is involved in the catalytic reaction.

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Section: Articlementioning

confidence: 97%

Ruthenium-Catalyzed Intramolecular Amination Reactions of Aryl- and Vinylazides

et al. 2009

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“…Favoured solvents are CCl 4 or CHCl 3 while CH 2 Cl 2 and acetone are sometimes less satisfactory (Table 2.3) [311][312][313]. A stoicheiometric RuO 4 /CCl 4 reagent is superior to CrO 3 /py or Pb(OAc) 4 for carbohydrate oxidations [313].…”

Section: Carbohydratesmentioning

confidence: 97%

“…For the cis-dihydroxylation of protected 1L- 4 itself is also effective and is likely to be the principal catalyst [348]. The system RuCl 3 / Na(BrO 3 )/aq.…”

Section: Miscellaneous Carbohydrate Oxidationsmentioning

confidence: 99%

“…M Na 2 (CO 3 ) [121]; H: RuO 2 /aq. Na(IO 4 )/CCl 4 [34]; J: RuCl 2 (PPh 3 ) 3 / TEMPO/O 2 /C 6 H 5 Cl/100°C ( Fig. 1.41) [36,37] [46].…”

Section: Primary Alcohols To Aldehydes (mentioning

confidence: 99%

“…The first Ru-catalysed oxidation of an alcohol was reported in 1965 when Parikh and Jones used RuO 2 /aq. Na(IO 4 )/CCl 4 1 ( Table 2.3) [2] to oxidise secondary alcohol groups in carbohydrates.Oxidation of alcohols is the most frequently reviewed topic for Ru-catalysed oxidations [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. Mechanisms of alcohol oxidation by Ru complexes have been reviewed [21].…”

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confidence: 99%

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Oxidation of Alcohols, Carbohydrates and Diols

Griffith

2009

Catalysis by Metal Complexes

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This is one of the most important classes of oxidation effected by Ru complexes, particularly by RuO 4 , [RuO 4 ] − , [RuO 4 ] 2− and RuCl 2 (PPh 3 ) 3 , though in fact most Ru oxidants effect these transformations. The chapter covers oxidation of primary alcohols to aldehydes (section 2.1), and to carboxylic acids (2.2), and of secondary alcohols to ketones (2.3). Oxidation of primary and secondary alcohol functionalities in carbohydrates (sugars) is dealt with in section 2.4, then oxidation of diols and polyols to lactones and acids (2.5). Finally there is a short section on miscellaneous alcohol oxidations in section 2.6.In this chapter the first of the two most important categories of oxidations catalysed by Ru complexes (the other being alkene and alkyne oxidations in Chapter 3) are considered. The approach in this and subsequent chapters differs from that of Chapter 1, concentrating here on the substrate rather than on the oxidant. The text is divided into the categories of alcohols and their oxidations. There are summaries in section 2.3.6 of systems of limited applicability which are mentioned only in Chapter 1, and in section 2.3.7 of large-scale (>1 g) oxidations.The first oxidations of alcohols by stoicheiometric RuO 4 /H 2 O were reported in 1958, of primary alcohols to aldehydes or carboxylic acids and secondary alcohols to ketones [1]. The first Ru-catalysed oxidation of an alcohol was reported in 1965 when Parikh and Jones used RuO 2 /aq. Na(IO 4 )/CCl 4 1 ( Table 2.3) [2] to oxidise secondary alcohol groups in carbohydrates.Oxidation of alcohols is the most frequently reviewed topic for Ru-catalysed oxidations [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. Mechanisms of alcohol oxidation by Ru complexes have been reviewed [21].

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Ruthenium: Inorganic & Coordination ChemistryBased in part on the article Ruthenium: Inorganic & Coordination Chemistry by Bruno Chaudret & Sylviane Sabo‐Etienne which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Sabo-Étienne¹,

Grellier²

2005

Encyclopedia of Inorganic Chemistry

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This article presents an overview of the inorganic and coordination chemistry of ruthenium. Since the first edition of the encyclopedia in 1994, the field has seen a huge growth. We have attempted to select the most useful data for the readers not familiar with this topic and to detail the most promising systems for future developments. Key data and recent highlights are thus presented for seven classes of compounds incorporating the following ligands: (1) Halides: RuCl 3 ·xH 2 O is by far the most useful starting material in ruthenium chemistry. (2) Oxygen‐donor ligands: this area is dominated by the chemistry of oxo complexes, with many applications in catalysis. (3) Sulfur‐donor ligands: potential applications are found in medicinal chemistry as antitumor agents and as radiosensitizers. (4) Nitrogen‐donor ligands: they represent the most important class of compounds in ruthenium chemistry. Supramolecular chemistry dominates, with photo‐redox processes and a wide range of applications being investigated from solar energy conversion to bioapplications. Ammines and bipyridines (and related ligands) are key ligands in this area. A great variety of inorganic architectures have been designed to assemble molecular machines and to favor interactions with DNA. (5) Phosphorus‐donor ligands: this class of compounds is at the origin of a rich organometallic chemistry, and the resulting complexes are often used as precursors in homogeneous catalysis. The design of new ligands for the improvement of catalytic performances is an active area of research. (6) Group 14 ligands: this field is dominated by the reactivity with silanes. New bonding modes, concepts, and applications have been disclosed. (7) Hydride ligands: the most recent developments concern the chemistry of dihydrogen complexes. The formation of dihydrogen bonds should have important consequences on the selectivity and stereochemistry in many catalytic processes. Finally, the last section is devoted to polynuclear complexes, with the new developments in the field of nanoparticles.

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Ruthenium and Osmium: High Oxidation States

Cited by 18 publications

References 558 publications

Ruthenium-Catalyzed Intramolecular Amination Reactions of Aryl- and Vinylazides

Ruthenium-Catalyzed Intramolecular Amination Reactions of Aryl- and Vinylazides

Oxidation of Alcohols, Carbohydrates and Diols

Ruthenium: Inorganic & Coordination ChemistryBased in part on the article Ruthenium: Inorganic & Coordination Chemistry by Bruno Chaudret & Sylviane Sabo‐Etienne which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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