Ruthenium complexes carbonyl chlorides

Dr. Halpern I don t know whether this is relevant to the first reaction or not, but we have also been struggling with the study of various reactions of ruthenium chlorides including ruthenium(II) chloride for a long time. Among the reactions studied is the formation of olefin and carbonyl complexes of ruthenium(II). These form readily in aqueous solution, and are fairly stable. James and Kemp, working on these systems in my laboratory have studied in some detail the kinetics of the reactions ... 

The product of stannous chloride and the carbonylated ruthenium chloride solution gives a cationic complex with diethyl sulfide (169). 

Copper(I) triflate was used as a co-catalyst in a palladium-catalyzed carbonylation reaction (Sch. 27). The copper Lewis acid was required for the transformation of homoallylic alcohol 118 to lactone 119. It was suggested that the CuOTf removes chloride from the organopalladium intermediate to effect olefin complexation and subsequent migratory insertion [60]. Copper(I) and copper(II) chlorides activate ruthenium alkylidene complexes for olefin metathesis by facilitating decomplexation of phosphines from the transition metal [61]. 

Ru(II), Ru(I) and Ir(I) in an aqueous medium (90). Data for the different complexes are shown in Table II. The highest conversion is observed with the ruthenium(II) complexes, which correlates with the facility of Ru complexes to catalyze other hydrogen transfer reactions. The complex PdCl2(TPPMS)2 has been used as a two-phase aqueous-organic catalyst for the carbonylation of allylic chlorides (Eq. 30) 91). The reaction pro-... 

Electrolysis of monomeric mono-bipyridine bis-carbonyl ruthenium(II) complexes bearing two tram leaving groups (e g. chloride anions or solvent molecules) generate at the working electrode a strongly adherent deep-blue film (Fig. 2A). This modified electrode demonstrate outstanding catalytic activity for the reduction of CO2 to CO (Fig. 2B) and was introduced in an effort to overcome the above limitations [10]. The overpotential was decreased to about 0.8V, and selective and quantitative formation of CO was obtained in aqueous electrolyte. 

Carbonylchlorohydridoruthenium complexes are often formed by the reduction of ruthenium chloride with alcohol in the presence of tertiary phosphines. The carbonyl ligand is derived from the alcohol just as Vaska s complex, lrCl(CO)(PPh3)2, is formed from (N H4)2lrCl6, PPh3 and alcohols. The carbonyl ligand is always located trans to... 

Much use has also been made of the zero-valent metal complexes as metal precursors, where it is thought advisable to avoid chloride or other possible harmful ions the carbonyls of ruthenium, rhodium, osmium, and iridium (of which there are many) have been used either as vapour if that is possible, or more often as solutions in organic solvents. °° ° ° Acetylacetonate (acac) complexes and r-allylic complexes have also been used. The term chemical vapour deposition (CVD) is used when the vapour of a volatile complex reacts with a support... 

Preliminary results of the reaction between vanadium(iii)-tetrasulpho-phthalocyanine complex with oxygen have been reported these data were compared with those obtained for the corresponding reaction of the hexa-aquo complex ion. The oxidation of methyl ethyl ketone by oxygen in the presence of Mn"-phenanthroline complexes has been studied Mn " complexes were detected as intermediates in the reaction and the enolic form of the ketone hydroperoxide decomposed in a free-radical mechanism. In the oxidation of 1,3,5-trimethylcyclohexane, transition-metal [Cu", Co", Ni", and Fe"] laurates act as catalysts and whereas in the absence of these complexes there is pronounced hydroperoxide formation, this falls to a low stationary concentration in the presence of these species, the assumption being made that a metal-hydroperoxide complex is the initiator in the radical reaction. In the case of nickel, the presence of such hydroperoxides is considered to stabilise the Ni"02 complex. Ruthenium(i) chloride complexes in dimethylacetamide are active hydrogenation catalysts for olefinic substrates but in the presence of oxygen, the metal ion is oxidised to ruthenium(m), the reaction proceeding stoicheiometrically. Rhodium(i) carbonyl halides have also been shown to catalyse the oxidation of carbon monoxide to carbon dioxide under acidic conditions ... 

Fig. 12 Carbon monoxide releasing compounds a manganese decacarbonjd b tricar-bonjdruthenium chloride dimer c a ruthenium-glycinate complex d iron carbonyl nucleoside analogues, TDSO = thex)4dimeth)4sil)4oxy...

Gold chloride forms an unstable complex with cyclo-octatetraene at low temperatures. This decomposes at — 20°C to l,2-dichlorocyclo-octa-3,5,7-triene, which gradually cyclizes to (562). In an attempt to form pentalene-metal complexes, cyclo-octatetraene was reduced to a mixture of trienes and bicyclo [4,2,0] octadiene, which was then treated with substituent ruthenium carbonyls, affording a variety of complexes, including (563). °... 

Oro and co-workers have shown that the one-pot reductive carbonylation of RuCls n-HjO with zinc, in the presence of a pyrazole derivative, yields dinuclear, pyrazolato-bridged, carbonyl complexes. To our knowledge, this was the first report on a facile, one-step synthesis of substituted carbonyl clusters, starting from ruthenium chloride. The one-pot synthetic route described here gives [PPN][HRu3(CO)n] in a yield of 83%, with respect to RUCI3 n-H20 as the starting material. 

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