Ruthenium-substituted

The ruthenium-substituted sandwich-type POM WZnRu2(OH)(H20)(A W9034)2]11 (X- Zn2+ or Co2+, Figure 13.1) catalyzed the selective hydroxylation of adamantane with Oz as an oxidant[58,59] ... 

Figure 13.4 Proposed catalytic cycle for activation of molecular oxygen and substrate by the ruthenium-substituted sandwich-type [WZnRu23 (XW90 34)2]11 (X=Zn2+ or Co2 ). (From Neumann, R., and Dahan, M., Nature, 388, 353, 1997 and Neumann, R., and Dahan, M., J. Am. Chem. Soc., 120, 11969, 1998.)...

The mono-ruthenium-substituted silicotungstate, [SiWn039Ru3+(H20)]5, synthesized by reaction of the lacunary POM Si Vn039 x with Ru3+ in acetone, was an efficient catalyst for the... 

According to the patent literature, Ru02 can be used as a stoichiometric oxidant in aldehyde formation.648 RuC13649 and a ruthenium-substituted heteropoly anion [SiRu(H20)Wn0395-]650 651 have been found to serve as a selective catalyst in this oxidation. H202649 and NaI04650 651 as oxidants, or electrochemical oxidation651 have been used. 

Table 1 Oxidation of alkanes with molecular oxygen catalysed by ruthenium-substituted-silico tungstate 1...

Table 6 Ruthenium-substituted polyoxometalates as catalysts for the oxidation of alcohols...

Very few methods have been reported for direct aerobic oxidation of alkanes using a perfluorinated ruthenium catalyst [Ru30(0C0CF2CF2CF3)6(Et20)3] [120c] and a ruthenium-substituted polyoxometalate [WZnRu2(0H)(H20)(ZnW9034)2] (Eqs. 3.102 and 3.103) [159, 160[. 

A related chemistry was reported by Weber with iron- and ruthenium-substituted diphosphenes and sulfur ylides. Thus, the presence of l,2-diphosphaspiro[2.2]pentane system linked to the metal through an Fe—P bond was confirmed by x-ray structure <87JOM(327)C63, 880M978). The... 

Perhaps the most important synthesis parameter affecting the crystallization of pyrochlore from alkaline solution is the oxidizing potential within the reaction medium. It is observed that this parameter has dramatic effects on both crystallinity and extent of ruthenium substitution by Pb . For example, a synthesis in which O2 is bubbled into the reaction medium will yield a well crystallized pyrochlore 2-3 times faster than a synthesis where O2 sparging is not provided. Crystalline pyrochlores cannot be obtained under any synthesis conditions (except those that are electrochemically assisted) when N2 sparging is used. The necessity for relatively oxidizing conditions in order to yield crystalline expanded pyrochlores is consistent with the hypothesis that these pyrochlores do... 

R. Neumann and M. Dahan, A Ruthenium-Substituted Polyoxometalate as an Inorganic Dioxygenase for... 

Khenkm AM, Elfemenko I, Weiner L et al (2010) Photochemical reduction of carbon dioxide catalyzed by a ruthenium substituted polyoxometalate. Chem A Eur J 16 1356-1364... 

Beyond the two mechanistic themes presented above, that is, autooxidation and redox-type reactions involving electron transfer, a ruthenium-substituted sandwich -type polyoxometalate was shown to be a catalyst for oxidation by a dioxygenase -type mechanism as outlined in Scheme 9.13 [125]. 

Cunningham M, McCrate A, Nielsen M, Swavey S (2009) Highly efficient visible-hght-induced photocleavage of DNA by a ruthenium-substituted fluorinated porphyrin. Eur J Inorg Chem 11 1521-1525... 

Ruthenium-substituted hydroxyapatite ((RuCl)2Cag(P04)6(0H)2) [65], the modified nafion resin 17 (Fig. 6) [66] and a series of ruthenium nanoparticles supported... 

Fig. 7 Schematic representation for the synthesis of the tetra-ruthenium-substituted POM by the reaction of [Y-SiWioOae] with (a) RuCL and (b) [Ru20Clio] as precursors [167, 171]...

Efficient oxidative sp C-H hydroxylations on arenes bearing weakly coordinating amides were accomplished with DIAB as the oxidant and a ruthenium(II) biscarboxylate, [Ru(02CMes)2(p-cymene)], as a catalyst. Mechanistic studies provided support for a reversible C-H bond metalation step. A 2 1 complex formed between a non-planar Mo(V)-porphyrin complex ([Mo(DPP)(0)]+, DPP = dodecaphenylporphyrin) and a ruthenium-substituted Keggin-type het-eropolyoxometalate (Ru-POM), [SiWn039Ru (DMS0)] , acts as an efficient catalyst for oxidation of benzyl alcohols with iodosobenzene as an oxidant. The kinetic... 

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