Other Complexes of Ruthenium

Ruthenium, in its normal oxidation states of II and III, forms a wide range of complexes with most available donor atoms, of which a representative selection are mentioned below. 

The structures of [Ru(HC0NMe2)6](CF3S03)x (x = 2,3) show a contraction in Ru-O distance from 2.088 A to 2.02 A on passing from the +2 to the +3 oxidation state [133a], 

There is a wide range of diketonates, such as Ru(acac)3, with octahedral coordination [133b] (they do not seem, however, to be oxidized to the +4 state this is possible with osmium) similarly several salts of the tris(oxalato) complex Ru(C204)3 have been isolated. 

Complexes of pyridine and substituted pyridines, mainly in the +2 state, have been made [134]  

The reaction of the (necessarily) m-oxalato complex with HCI in the last example, ensures the m-configuration for the chloro complex on recrystallization, the thermodynamically more stable trans-isomer forms. tran.s-Rupy4Cl2 has Ru—N 2.079 A and Ru—Cl 2.405 A. An imidazole complex (imH) tra .v-[RuCl4(im)2] shows promise as a tumour inhibitor and is currently undergoing preclinical trials [135]. 

Many ruthenium complexes with nitrile ligands also feature tertiary phosphines, but simpler complexes can be synthesized [136] 

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Ruthenium(IV) produces few other complexes of interest but osmium(IV) yields several sulfito complexes (e.g. [0s(S03)6] and substituted derivatives) as well as a number of complexes, such as [Os(bipy)Cl4] and [Os(diars)2X2] (X = Cl, Br, I), with mixed halide and Group 15 donor atoms. The iron analogues of the latter complexes (with X = Cl, Br), are obtained by oxidation of... 

Ruthenium probably forms more nitrosyl complexes [115] than any other metal. Many are octahedral Ru(NO)Xs systems, where X5 can represent a combination of neutral and anionic ligands these contain a linear (or very nearly) Ru-NO grouping and are regarded as complexes of ruthenium(II). They are often referred to as (Ru(NO) 6 systems. 

Since the first report on the ferrocene mediated oxidation of glucose by GOx [69], extensive solution-phase studies have been undertaken in an attempt to elucidate the factors controlling the mediator-enzyme interaction. Although the use of solution-phase mediators is not compatible with a membraneless biocatalytic fuel cell, such studies can help elucidate the relationship between enzyme structure, mediator size, structure and mobility, and mediation thermodynamics and kinetics. For example, comprehensive studies on ferrocene and its derivatives [70] and polypy-ridyl complexes of ruthenium and osmium [71, 72] as mediators of GOx have been undertaken. Ferrocenes have come to the fore as mediators to GOx, surpassing many others, because of factors such as their mediation efficiency, stability in the reduced form, pH independent redox potentials, ease of synthesis, and substitutional versatility. Ferrocenes are also of sufficiently small size to diffuse easily to the active site of GOx. However, solution phase mediation can only be used if the future biocatalytic fuel cell... 

Tris(bpy) complexes of ruthenium(II) with pendant catechol units are represented by [Ru(bpy)2(114)], isolated as the BF4 salt. Interest in this fluorescent complex stems from its use as a potential skin sensitizer. " In the complex [Ru(bpy)2(115)] + (R = H), the deprotonated catechol unit can act as a binding site for other metal fragments, thereby forming homo- and... 

Mo(r75-C5H5)2H2] and [MoH dppe ]. Our studies of the di- and trihydride complexes of ruthenium and iridium, described above and published previously (27,35), and those of other workers (discussed at the beginning of this chapter), indicate that photoinduced elimination of molecular hydrogen is a common reaction pathway for di- and polyhydride complexes. To demonstrate the photoreaction s generality and its utility for generating otherwise unattainable, extremely reactive metal complexes, we have begun to study the photochemistry of polyhydride complexes of the early transition metals. We focused initially... 

Heavier metal ions and metal complexes can find sites on nitrogen atoms of the nucleic acid bases. Examples are the platinum complex cisplatin and the DNA-cleaving antibiotic neocarzinostatin (Box 5-B). Can metals interact with the n electrons of stacked DNA bases A surprising result has been reported for intercalating complexes of ruthenium (Ru) and rhodium (Rh). Apparent transfer of electrons between Ru (II) and Rh (III) over distances in excess of 4.0 nm, presumably through the stacked bases, has been observed,181 as has electron transfer from other ions.181a Stacked bases are apparently semiconductors.182... 

ECL from inorganic chromophores has been observed from a variety of transition metal complexes of ruthenium, osmium, palladium, platinum, and a few other transition metal chromophores, some of which are listed in Tables 2 and 3. For example, ECL has been observed from tetrakis(pyrophosphito)diplatinate(II),... 

Another interesting and potentially very useful group of calixarene-based anion receptors is represented by systems with appended transition metal complexes of 2,2-bipyridine units. Technically, these systems utilise classical hydrogen bonding interactions of amidic/urea functions hence, from this point of view, they do not differ from many other receptors. On the other hand, the covalent attachment of bipyridine complexes of ruthenium(II) or rhe-... 

In the following section, we discuss the basic mechanism of homogeneous hydrogenation by Wilkinson s catalyst, RhCl(PPh3)3. Many other complexes of rhodium as well as complexes of other metals such as ruthenium, platinum, lutetium, etc. have also been used as homogeneous, laboratory-scale, hydrogenation catalysts. The mechanisms in all these cases may differ substantially. 

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