Ruthenium perfluorinated

Fig. 2 Different orange-red luminescent layers for O2 sensing, a Indicator layer containing the tris(4,7-diphenyl-l,10-phenanthroline)ruthenium(II) dye adsorbed on CPG particles embedded in a poly(dimethylsiloxane) film [8]. b Perfluorinated (Nation) ionomer membrane doped with the same cationic dye. Although the former appears as a homogeneous material, even under the optical microscope, the luminescent indicator is actually sitting down in various domains as evidenced by its emission kinetics profile [9]...

Aqua(phosphine)ruthenium(II) complexes [121] are useful for activation of molecular oxygen, and catalytic oxidation of cyclohexene can be carried out with 1 atm of O2 [121a,bj. The ruthenium catalyst bearing perfluorinated 1,3-diketone ligands catalyzes the aerobic epoxidation of alkenes in a perfluorinated solvent in the presence of i-PrCHO [122]. Asymmetric epoxidations of styrene and stilbene proceed with 56-80% e.e. with ruthenium complexes 38-40 (Figure 3.2) and oxidants such as PhI(OAc)2, PhIO, 2,6-dichloropyridine N-oxide, and molecular oxygen [123-125]. 

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]. 

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[. 

Figure 14. (a) Structure of a zeolite-entrapped perfluorinated ruthenium phthalocyanine (RuFi6Pc) complex used in epoxidation reactions, (b) Comparison of turnover numbers for cyclohexane oxidation using ruthenium phthalocyanine (RuPc), RuFi Pc and zeolite X-entrapped RuFi Pc. 

Epoxidation of olefins was catalyzed by the ruthenium(II) complex of the above perfluorinated y3-diketone in the presence of 2-methylpropanal (Scheme 50). Unfunctionalized olefins were epoxidized with a cobalt-containing porphyrin complex, and epoxidation of styrene derivatives was catalyzed by chiral salen manganese complexes (248) (Scheme 50). In the latter case, chemical yields were generally high, however, the products showed low enantiomeric excess with the exception of indene (92% ee). [Pd(C7Fi5COCHCOC7Fi5)2] efficiently catalyzed the oxidation of terminal olefins to methyl ketones with f-butylhydroperoxide as oxidant in a benzene-bromoperfluoro-octane solvent system (Scheme 50). In all these reactions, the product isolation and efficient catalyst recycle was achieved by a simple phase separation. 

Balkus KJ Jr, Eissa M, Levado R (1995) Oxidation of alkanes catalyzed by aeolite-encapsulated perfluorinated ruthenium phthalocyanines. J Am Chem Soc 117 10753—10754 Ouyang J, Shigehara K, Yamada A, Anson FC (1991) Hexadecafiuoro- and octacyano phthalocyanines as electrocatalysts for the reduction of dioxygen. J Electroanal Chem 297 489-498... 

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