Arene ruthenium complex, with

An arene ruthenium complex with polymerizable side chains for the... 

AN ARENE RUTHENIUM COMPLEX WITH POLYMERIZABLE SIDE CHAINS FOR THE SYNTHESIS OF IMMOBILIZED CATALYSTS... 

Auzias M, Therrien B, Siiss-Fink G, Stepnicka P, Ang WH, Dyson PJ (2008) Ferrocenoyl pyridine arene ruthenium complexes with anticancer properties synthesis, structure, electrochemistry, and cytotoxicity. Inorg Chem 47 578-583... 

Prochiral 3-substituted 2ff-azirines can be reduced to the corresponding aziridines by an in situ prepared arene ruthenium complex, with the amino alcohol, depicted in Figure 83, as the chiral ligand (343). It is interesting to point out that 2-propanol was used as the hydrogen donor. Yield up to 92% and enantiose-lectivities up to 72% ee were achieved. 

Freudenreich J, Furrer J, Siiss-Fink G, Therrien B. Template-directed synthesis of hexa-nuclear arene ruthenium complexes with trigonal-prismatic architecture based on 2,4,6-tris (3-pyridyl)triazine Ligands. Organometallics 2011 30 942-51. 

A large number of strapped arene complexes of ruthenium(ll) have been prepared by treatment of [RuCl2(il6-arene)]2 complexes with tertiary phosphines of the type R2P Ar in which an aromatic group is separated from the phosphorus atom by a two- or three-atom chain. In the first step, which usually occurs at or just above... 

Wang F, Bella J, Parkinson JA, Sadler PJ (2005) Competitive reactions of a ruthenium arene anticancer complex with histidine, cytochrome c and an oligonucleotide. J Biol Inorg Chem 10 147-155... 

Wang F, Weidt S, Xu J, Mackay CL, Langridge-Smith PRR, Sadler PJ (2008) Identification of clusters from reactions of ruthenium arene anticancer complex with glutathione using nanoscale liquid chromatography fourier transform ion cyclotron mass spectrometry combined with 180-labeling. J Am Soc Mass Spectrom 19 544-549... 

Fig. 7 Examples of ruthenium(II)-arene and osmium(II)-arene paullone complexes with high in vitro anticancer activity...

The first example of an optically active arene ruthenium complex was obtained by Brunner and Gastinger (68). The reaction of la with HgMe2 (44) and then (R)-(+)Ph2PNHCH(Me)Ph afforded a pair of diastereoisomers, 116 and 117, which were separated by chromatography (68,69) (Scheme 9). Complexes 116 and 117 (X = Cl) react with SnCl2 to give complexes 118 and 119, but the stereoselectivity depends on reaction... 

Cyclophane ruthenium complexes have been prepared by the methods developed to make arene ruthenium complexes (Section II,A). Treatment of the solvated complexes of type 7, obtained from the dimers 1 and silver tetrafluoroborate in acetone, with 1 equiv of cyclophanes a-j in the presence of trifluoroacetic acid gives the double-layered (i76-arene)-(i76-cyclophane)ruthenium(II) complexes 263 in good yield (Scheme 26, p. 222). When 7 is used in excess, the triple-layered complex 264 is formed (159-162). 

Arene ruthenium complexes are used frequently in metal-mediated organic synthesis for a wide range of reactions.5 For the purposes of our studies we have focused attention mainly on enol formate synthesis as a representative reaction for comparing the activity of 2 with its non-supported analogue 5. As with the supported cobalt complex, we find that attachment of 5 to a polymer support has little effect in its catalytic activity with a range of enol formates being prepared in high yield. 

In this section, we will review the nature and chemical reactivities of several kinds of ruthenium complexes under the following headings ruthenium carbonyl complexes, dichlororuthenium complexes, chlorohydrido complexes, dihydridoruthenium complexes, ruthenium complexes with chiral ligands, ruthenium complexes with cyclopentadienyl ligands, and ruthenium arene/diene complexes. 

Ruthenium Complexes with Arene/Diene Ligands... 

In addition to transfer hydrogenation reactions, arene ruthenium complexes also display excellent activity in the catalytic hydrogenation of olefins and alkynes including asymmetric reduction [40]. Remarkably, this process occurs under milder conditions, than required for catalysis with the dissociation of arene-metal bond. Lately, arene iridium complexes have also been found to be effective hydrogenation catalysts [41 ]. It is noteworthy that iridium can also promotes addition to the carbon-nitrogen double bond. 

Enantioselective cyclopropanation is currently being explored. The ruthenium complex shown previously in Figure 7 also reacts with EDA and styrene to afford a transxis ratio of 4 1, with 46% ee of the trans isomer. The cis isomer is nearly racemic (<10% ee). The use of four-substituted stjrrene derivatives dramatically increases the diastereoisomeric excess of the trans isomer, with 4-fluorostyrene giving an 11 1 ratio, with 50% ee (74). Conversely, as shown in Figure 21, the porphyrin-like [RuCl(PNNP)]+ precatalyst reacts with EDA/ styrene to afford the cis isomer at a ratio of 10 1, with an enantiomeric excess of 87% (76). These types of ruthenium complexes have also been described as epoxi-dation catalysts above clearly there are mechanistic similarities between the oxo-and carbene- intermediates, which could help elucidate the reasons behind such variable enantioselectivity. Other ruthenium complexes that catalyze cyclopropanation include CpRu(II) catalysts, arene ruthenium complexes, and ruthenium-salen complexes. Cp Ru(cod)Cl is also known to catalyze the related reaction of diazo compounds with alkynes, affording the corresponding 1,3-diene (Figure 22) (77). 

Recently, computations on ruthenium complexes with nucleobases were published by Futera (Futera et al. 2009). In his comprehensive study interactions of piano-stool ruthenium met-allodrug with nucleobases were investigated. In the same study the reaction profile of the chloro-ligand replacement by water molecule and the role of the arene-ring size were also explored. From the point of this review, an important part of Futera s study deals with interactions of Ru(II) with various sites of all the nudeobases in vacuum and under implicit solvent model. For the optimized structures, the bonding and stabilization energies were determined. 

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