Ligand-based reduction structures

SnCl4 gives 1 1 (297) and 2 1 (298) adducts with Ni(dto)2- and their structures were determined by X-ray analysis,2146 Unlike the parent K2Ni(dto)2 complex, the heterometal complexes (297) and (298) undergo reversible electrochemical reductions which are mainly ligand-based.214 ... 

The first structural report on a phthalocyanine complex concerned [Ni(pc)J (Table 110 I).2878 In the crystal lattice of this compound the square planar macrocycles are arrayed in slipped stacks such that the distance between the molecular planes along the perpendicular direction is 388 pm. [Ni(pc)] may be prepared by a variety of methods 2873,2871 2880 a convenient one is heating a foil of elemental nickel in o-cyanobenzamide at 270 °C (Scheme 60).2881 [Ni(pc)] is insoluble in the most common organic solvents, but soluble in concentrated sulfuric acid from which it is reprecipitated unchanged upon dilution. This complex is thermally very stable and may be sublimed in vacuo. The reduction of [Ni(pc)] can be accomplished by chemical or electrochemical methods and results in ligand-based reduced anions [Ni(pc)]" ( = 1, 2). Analogously, the electrochemical oxidation results in the oxidized ligand. 3... 

Reductions are generally considered to be ligand-based and up to three reductions are often possible. Both the monocationic [Ru(bpy)3]+ 65 and the neutral Ru(bpy)366 have been isolated and structurally characterized by X-ray diffraction. 

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