6- -2,2 -bipyridine, formation ruthenium complexes

A chromophore such as the quinone, ruthenium complex, C(,o. or viologen is covalently introduced at the terminal of the heme-propionate side chain(s) (94-97). For example, Hamachi et al. (98) appended Ru2+(bpy)3 (bpy = 2,2 -bipyridine) at one of the terminals of the heme-propionate (Fig. 26) and monitored the photoinduced electron transfer from the photoexcited ruthenium complex to the heme-iron in the protein. The reduction of the heme-iron was monitored by the formation of oxyferrous species under aerobic conditions, while the Ru(III) complex was reductively quenched by EDTA as a sacrificial reagent. In addition, when [Co(NH3)5Cl]2+ was added to the system instead of EDTA, the photoexcited ruthenium complex was oxidatively quenched by the cobalt complex, and then one electron is abstracted from the heme-iron(III) to reduce the ruthenium complex (99). As a result, the oxoferryl species was detected due to the deprotonation of the hydroxyiron(III)-porphyrin cation radical species. An extension of this work was the assembly of the Ru2+(bpy)3 complex with a catenane moiety including the cyclic bis(viologen)(100). In the supramolecular system, vectorial electron transfer was achieved with a long-lived charge separation species (f > 2 ms). 

The ruthenium complexes were attached to the specified cysteine by formation of a thioether linkage between the sulfur atom of cysteine and the methylene carbon of one of the bipyridine ligands. The reaction makes use of complexes that contain 4-bromomethyl-4 -methylbipyridine, as indicated. 

Srimani D, BalaramanE, HuP, Ben-David Y, Milstein D (2013) Formation of tertiary amides and dihydrogen by dehydrogenative coupling of primary alcohols with secondary amines catalyzed by ruthenium bipyridine-based pincer complexes. Adv Synth Catal 355 2525... 

Photocatalytic enantioselective oxidative arylic coupling reactions have been investigated by two different groups. Both studies involved the use of ruthenium-based photocatalysts [142, 143]. In 1993, Hamada and co-workers introduced a photostable chiral ruthenium tris(bipyridine)-type complex (A-[Ru(menbpy)3]2+) 210 possessing high redox ability [143]. The catalytic cycle also employed Co(acac)3 211 to assist in the generation of the active (A-[Ru(menbpy)3]3+) species 212. The authors suggested that the enantioselection observed upon binaphthol formation was the result of a faster formation of the (R)-enantiomer from the intermediate 213 (second oxidation and/or proton loss), albeit only to a rather low extent (ee 16 %) (Scheme 54). 

The contribution of pulse radiolysis to general chemistry is very significant, and this is exemplified by the following studies of transition metal complexes. The reduction of tris(2,2 -bipyridine)ruthenium(III) ion by the hydrated electron was the first example of this type of reaction to show clearly the formation of a product in an electronically excited state [80] ... 

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. 

The challenging photochemical reduction of carbon dioxide to formate is catalyzed by Ru" [111] (cf. Section 3.3.4). For example, with the 2,2 -bipyridine-ruthenium(II) complex the active species is formed by photolabilization. Water renders the system more efficient with quantum yields up to 15%. Methanol is the photoproduct when CO2 is reduced with Ti02 in propene carbonate/2-propanol... 

Electropolymerization of 4-Vinylpyridine Complexes. Investigations of Structural and Electronic Influences on Thin Film Formation. The recent discovery of the reductive polymerization of complexes containing vinylpyridyl ligands (lg), such as Ru -(bpy)2(vpy)22+ has led to the preparation of homogeneous thin layers of very stable electroactive polymers. This method has been extended to 4-vinyl-4 -methyl-2,2 -bipyridine (lg, 21a) and 4-vinyl-l,10-phenanthroline (21b) on both ruthenium and iron. In the following section we discuss our results on thin films derived from the polymerizable ligands BPE and the trans-4 -X-stilbazoles, (4 -X-stilb X - Cl, OMe, CN and H). 

An example for the second type of crypto-hydroxyl radical formation has very recently been reported to exist in an in vitro model system for water oxidation consisting of tris(bipyridine)-ruthenium(III)-salts99). In the complex an internal charge... 

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