Dioxoruthenium complex

Although the chiral ketoiminatomanganese(lll) complexes were reported to catalyze the asymmetric aerobic alkene epoxidations, an aldehyde such as pivalaldehyde is required as a sacrihcial reducing agent. Groves reported that the dioxo(porphyrinato)ruthenium complexes 31, prepared with m-chloroperoxyben-zoic acid, catalyzed the aerobic epoxidation without any reductant. " On the basis of these reports, Che synthesized the optically active D4-porphyrin 35 and applied it to the truly aerobic enantioselective epoxidation of alkenes catalyzed by the chiral frani-dioxo (D4-porphyrinato)ruthenium(Vl) complex. The dioxoruthenium complex catalyzed the enantioselective aerobic epoxidation of alkenes with moderate to good enantiomeric excess without any reductant. In the toluene solvent, the turnovers for the epoxidation of T-(3-methylstyrene reached 20 and the ee of the epoxide was increased to 73% ee. 

Novel practical methods using various reagents, such as [Co(OAc)Br],1355 sulfur trioxide,1356 or ds-dioxoruthenium complexes,1357 were developed to transform alkynes to 1,2-diketones. Radical-catalyzed aerobic oxidation using A-hydro-xyphthalimide combined with a transition metal (Co, Cu, or Mn) affords a,P-acetylenic ketones in good yields.1358 Oxidation by the HOF. acetonitrile complex yields diketones, ketoepoxides, or cleavage products.1359 Ozonolysis of acetylenes combined with trapping techniques affords to isolate various derivatives.1360,1361 New information for the ozonolysis of acetylene was acquired by quantum-chemical investigatons.1362... 

Zeolite-encapsulated perfluorinated ruthenium phthalocyanines catalyze the oxidation of cyclohexane with t-BuOOH [146]. A dioxoruthenium complex with a D4-chiral porphyrin ligand has been used for the enantioselective hydroxylation of ethylbenzene to give a-phenylethyl alcohol with 72% e.e. [147]. 

PREPARATION OF THE rRAAA-DIOXORUTHENIUM(VI) COMPLEXES WITH D2 SYMMETRIC PORPHYRINS (H2L1 3)[7]... 

These tru 5-dioxoruthenium(VI) complexes have characteristic UV-vis absorption spectra. The fj-saturated nature of the macrocyclic tertiary amine ligands enables the high-energy metal-localized transition to be observed. " The weak vibronic structured band at 370-400nm has been assigned to (0 ) —> Ru charge transfer transition that is vibronically coupled to the... 

In general, tertiary amines are better cr-donors than pyridines. Hence dioxoruthenium(VI) complexes of macrocyclic tertiary amines are more stable and weaker oxidants than those of polypyridyls. 

The electrochemistry of dioxoruthenium(VI) and dioxoosmium(VI) complexes with polypyridyl and macrocyclic tertiary amine ligands has been extensively studied by cyclic voltammetric techniques. In general, cA-dioxo species have higher reduction potentials than the corresponding trans-Aiaxo species. " " For the trans-Aioxo species, the d, orbital ordering... 

The tra x-[Ru (0)2(por)] complexes are active stoichiometric oxidants of alkenes and alkylaro-matics under ambient conditions. Unlike cationic macrocyclic dioxoruthenium I) complexes that give substantial C=C bond cleavage products, the oxidation of alkenes by [Ru (0)2(por)] affords epoxides in good yields.Stereoretentive epoxidation of trans- and cw-stilbenes by [Ru (0)2(L)1 (L = TPP and sterically bulky porphyrins) has been observed, whereas the reaction between [Ru (0)2(OEP)] and cix-stilbene gives a mixture of cis- and trani-stilbene oxides. Adamantane and methylcyclohexane are hydroxylated at the tertiary C—H positions. Using [Ru (0)2(i)4-por)], enantioselective epoxidation of alkenes can be achieved with ee up to 77%. In the oxidation of aromatic hydrocarbons such as ethylbenzenes, 2-ethylnaphthalene, indane, and tetrahydronaphthalene by [Ru (0)2(Z>4-por )], enantioselective hydroxylation of benzylic C—H bonds occurs resulting in enantioenriched alcohols with ee up to 76%. ... 

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