Radical ligands

An optically transparent thin-layer electrode (OTTLE) study18 revealed that the visible spectra of the reduced forms of [Ru(bipy)3]2+ derivatives can be separated into two classes. Type A complexes, such as [Ru(bipy)3]2+, [Ru(L7)3]2+, and [Ru(L )3]2+ show spectra on reduction which contain low-intensity (e< 2,500 dm3 mol-1 cm-1) bands these spectra are similar to those of the reduced free ligand and are clearly associated with ligand radical anions. In contrast, type B complexes such as [Ru(L8)3]2+ and [Ru(L9)3]2+ on reduction exhibit spectra containing broad bands of greater intensity (1,000 [Pg.584]

Most of the kinetic models predict that the sulfite ion radical is easily oxidized by 02 and/or the oxidized form of the catalyst, but this species was rarely considered as a potential oxidant. In a recent pulse radiolysis study, the oxidation of Ni(II and I) and Cu(II and I) macrocyclic complexes by SO was studied under anaerobic conditions (117). In the reactions with Ni(I) and Cu(I) complexes intermediates could not be detected, and the electron transfer was interpreted in terms of a simple outer-sphere mechanism. In contrast, time resolved spectra confirmed the formation of intermediates with a ligand-radical nature in the reactions of the M(II) ions. The formation of a product with a sulfonated macrocycle and another with an additional double bond in the macrocycle were isolated in the reaction with [NiCR]2+. These results may require the refinement of the kinetic model proposed by Lepentsiotis for the [NiCR]2+ SO/ 02 system (116). 

The redox properties elicited for Rh(bpy)3 + and its congeners are thus entirely consistent with the description of these species as bound-ligand radicals. On the other hand, the disproportionation reactions eq 2-6 are not known to be characteristic of ligand-centered radicals, but are consistent with behavior expected for rhodium(II). Furthermore the substitution lability deduced for Rh(bpy)3 + and Rh(bpy)2 +> while consistent with that expected for Rh(II), is orders of magnitude too great for Rh(lII). Finally the spectrum observed for the intermediate Rh(bpy)3 + is not that expected for [RhIII(bpy)2(bpy")]2+. The spectrum measured has an absorption maximum at 350 nm with e 4 x 10 M 1 cm l and a broad maximum at 500 nm with e = 1 x 1()3 M 1 cm l. The spectra of free and bound bpy radical anions are quite distinctive (23.35-38) very intense absorption maxima (e 1 x 10 to 4 x 10 M - cm l) are found at 350-390 nm and are accompanied by less intense maxima (e 5 x 10 cm ) at 400 to 600 nm. While the Rh(bpy)3 +... 

Oxidation of d V(V) complexes must occur at the ligands. Although many oxidations are irreversible, some reversible processes are known. For example, the square-pyramidal bimetallic complex shown in Fig. 23 has two reversible oxidations Ef" = —0.05 and 0.37 V versus Cp2Fe/MeCN), the first of which results in a cationic ligand radical species, on the basis of its Ef value, its EPR spectrum, and UV-vis data [111]. The complex also shows two closely spaced reductions (Ef =—1.2(> and —1.36 V... 

As regards other coordination compounds of silver, electrochemical synthesis of metallic (e.g. Ag and Cu) complexes of bidentate thiolates containing nitrogen as an additional donor atom has been described by Garcia-Vasquez etal. [390]. Also Marquez and Anacona [391] have prepared and electrochemically studied sil-ver(I) complex of heptaaza quinquedentate macrocyclic ligand. It has been shown that the reversible one-electron oxidation wave at -1-0.75 V (versus Ag AgBF4) corresponds to the formation of a ligand-radical cation. Other applications of coordination silver compounds in electrochemistry include, for example, a reference electrode for aprotic media based on Ag(I) complex with cryptand 222, proposed by Lewandowski etal. [392]. Potential of this electrode was less sensitive to the impurities and the solvent than the conventional Ag/Ag+ electrode. 

Ni(III) complexes often exhibit equilibrium with Ni(II) ligand radical species. For example, the Ni(III) complex of lacunar cyclidene is octahedral [NimL(CH3CN)2]3+ at low temperature, but at high temperature it transforms into the Ni(II) complex with an oxidized ligand radical [NinL+]3+, identifiable by the absorption at 590 nm. The Ni(III) complexes and Ni(II) species with an oxidized ligand radical exhibit a thermal equilibrium (Eq. 12) (105). 

TRI- AND TETRANUCLEAR CARBONYL-RUTHENIUM CLUSTER COMPLEXES CONTAINING ISOCYANIDE, TERTIARY PHOSPHINE, AND PHOSPHITE LIGANDS. RADICAL ION-INITIATED SUBSTITUTION OF METAL CLUSTER CARBONYL COMPLEXES UNDER MILD CONDITIONS... 

Dithiolenes have been found to stabilize nickel(III) and a number of structural investigations have been performed on nickel(III) dithiolene complexes. Structural data and physical properties of selected compounds are collected in Table 120. The EPR spectra of the [NiS4] unit have been extensively studied in order to decide whether the unpaired electron resides mainly on the metal or on the ligand3202,3203,3210,3212-3217 giving rise to a true nickel(III) complex (422) or to a nickel(II)-stabilized ligand radical complex (423). 

The mechanism summarized in equations (40)—(42) is applicable, with some modifications,92 94 to the CTTM photochemistry of Crm and Rh111 acidoammine complexes. Thus the primary photochemical step is formation of a substitutionally labile reduced metal species and an oxidized ligand radical. In most systems, however, no permanent redox chemistry occurs owing to the facile reoxidation of the metal. The only net photoprocess observed in these cases is substitution of one or more ligands.70 95... 

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