High-valent ruthenium complex

A high-valent ruthenium complex is also reported to cleave the sp C-H bond. RuCl3 -3H20 catalyzes the transformation of cyclic alkanes to the corresponding ketones in the presence of peracetic acid, where oxoruthenium species is considered to act as the active species. Alcohol, as a primary product in this oxidation reaction, is obtained as an intermediate in the presence of trifluoroacetic acid (Scheme 14.11) [25]. 

High-valent ruthenium oxides (e. g., Ru04) are powerful oxidants and react readily with olefins, mostly resulting in cleavage of the double bond [132]. If reactions are performed with very short reaction times (0.5 min.) at 0 °C it is possible to control the reactivity better and thereby to obtain ds-diols. On the other hand, the use of less reactive, low-valent ruthenium complexes in combination with various terminal oxidants for the preparation of epoxides from simple olefins has been described [133]. In the more successful earlier cases, ruthenium porphyrins were used as catalysts, especially in combination with N-oxides as terminal oxidants [134, 135, 136]. Two examples are shown in Scheme 6.20, terminal olefins being oxidized in the presence of catalytic amounts of Ru-porphyrins 25 and 26 with the sterically hindered 2,6-dichloropyridine N-oxide (2,6-DCPNO) as oxidant. The use... 

There are few well-characterized high-valent peroxo complexes of ruthenium and osmium, presumably because they decompose readily to give oxo complexes. 

One example which deserves special mention is the use of a percarboxylic acid such as peracetic acid, generated in situ by autoxidation of the corresponding aldehyde, developed by Murahashi and coworkers, see Eq. (1) [25-27]. These reactions are generally considered to involve high-valent oxoruthenium complexes, generated by reaction of the percarboxylic acid with the ruthenium catalyst, as the active oxidant. 

Ruthenium compounds are widely used as catalysts for hydrogen transfer reactions. These systems can be readily adapted to the aerobic oxidation of alcohols by employing dioxygen, in combination with a hydrogen acceptor as a cocatalyst, in a multistep process. These systems demonstrate high activity. For example, Backvall and coworkers [146] used low-valent ruthenium complexes in combination with a benzoquinone and a cobalt-Schiffs base complex. Optimization of the electron-rich quinone, combined with the so-called Shvo Ru-cata-lyst, led to one of the fastest catalytic systems reported for the oxidation of secondary alcohols (Fig. 4.59). 

Chaudret and coworkers synthesized an ortho-ruthenated acetophenone complex (26) having axial tricyclohexylphosphine ligands. Complex 26 showed almost no catalytic activity, and on the basis of this observation and the activity of 22, they proposed that the binding of the CO Hgand to the ruthenium suppresses the catalytic activity of the ruthenium complex. Fogg and coworkers prepared ortho-ruthenated benzophenone complex 27, which showed only low catalytic activity and was proposed to be a catalytic sink in the alkylation of aromatic ketones. Weber and coworkers synthesized a unique zero-valent ruthenium complex (23), which was effective for the alkylation of aromatic ketones. Subsequently, Whittlesey and coworkers synthesized complex 25, which did not catalyze the hydroarylation. However, the authors stated it was highly Hkely that alternative isomers of 25 could be involved in the catalytic pathways. Further hints toward this end came with the characterization of the two N,0-coordinated acetylpyrrolyl complexes 24 and 28. Complex 24 was found to be an active catalyst of the reaction but was shown to isomerize to its inactive isomer 28 at 80 °C. 

While major advances in the area of C-H functionalization have been made with catalysts based on rare and expensive transition metals such as rhodium, palladium, ruthenium, and iridium [7], increasing interest in the sustainability aspect of catalysis has stimulated researchers toward the development of alternative catalysts based on naturally abundant first-row transition metals including cobalt [8]. As such, a growing number of cobalt-catalyzed C-H functionalization reactions, including those for heterocycle synthesis, have been reported over the last several years to date (early 2015) [9]. The purpose of this chapter is to provide an overview of such recent advancements with classification according to the nature of the catalytically active cobalt species involved in the C-H activation event. Besides inner-sphere C-H activation reactions catalyzed by low-valent and high-valent cobalt complexes, nitrene and carbene C-H insertion reactions promoted by cobalt(II)-porphyrin metalloradical catalysts are also discussed. 

High-Valent Complexes of Ruthenium and Osmium Chi-Ming Che and Vivian Wing-Wah Yam... 

Other ruthenium-based catalysts for the aerobic oxidation of alcohols have been described where it is not clear if they involve oxidative dehydrogenation by low-valent ruthenium, to give hydridoruthenium intermediates, or by high-valent oxoruthenium. Masutani et al. [107] described (nitrosyl)Ru(salen) complexes, which can be activated by illumination to release the NO ligand. These complexes demonstrated selectivity for oxidation of the alcoholic group versus epoxidation, which was regarded as evidence for the intermediacy of Ru-oxo moieties. Their excellent alcohol coordination properties led to a good enantiomer differentation in the aerobic oxidation of racemic secondary alcohols (Fig. 19) and to a selective oxidation of primary alcohols in the presence of secondary alcohols [108]. 

The unique versatility of ruthenium as an oxidation catalyst continues to provide a stimulus for research on a variety of oxidative transformations. Its juxtaposition in the periodic table and close similarity to the biological redox elements, iron and manganese, coupled with the accessibility of various high-valent oxo species by reaction of lower-valent complexes with dioxygen make ruthenium an ideal candidate for suprabiotic catalysis. 

Other species. In a study by the Che group, it proved possible to prepare a composite complex that spans both categories. Thus, oxidation (either chemical or electrochemical) of the double-helical [Ru2L2(H20)2] (L = quinquepyridine) cation in aqueous solution results in a product containing both a photoactive ruthenium centre and a high-valent Ru=0 centre in the one complex. 

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