2,2 -Bipyridine complexes with metals

The ability of 2,2 -bipyridine and its derivatives to form complexes with metals and nonmetals is well known, and the subject has been thoroughly reviewed. Further discussion of this topic is outside the scope of this review. 

Coordination Compounds. A large number of indium complexes with nitrogen ligands have been isolated, particularly where Ir is in the +3 oxidation state. Examples of ammine complexes include pr(NH3)3] " [24669-15-6], prCl(NH3)] " [29589-09-1], and / j -pr(03SCF3)2(en)2]" [90065-94-4], Compounds of A/-heterocychc ligands include trans- [xCX py)][ [24952-67-8], Pr(bipy)3] " [16788-86-6], and an unusual C-metalated bipyridine complex, Pr(bipy)2(C, N-bipy)] [87137-18-6]. Isolation of this latter complex produced some confusion regarding the chemical and physical properties of Pr(bipy)3]3+ (167). 

Transition metal complexes with 2,2 -bipyridine ligands in anion-selective recognition and optical/electrochemical sensing 96CC689. 

There are more examples of a second type in which the chirality of the metal center is the result of the coordination of polydentate ligands. The easiest case is that of octahedral complexes with at least two achiral bidentate ligands coordinated to the metal ion. The prototype complex with chirality exclusively at the metal site is the octahedral tris-diimine ruthenium complex [Ru(diimine)3 with diimine = bipyridine or phenanthroline. As shown in Fig. 2 such a complex can exist in two enantiomeric forms named A and A [6,7]. The bidentate ligands are achiral and the stereoisomery results from the hehcal chirality of the coordination and the propeller shape of the complex. The absolute configuration is related to the handness of the hehx formed by the hgands when rotated... 

Ru 2,2 -bipyridine complexes can form a large number of colored compounds upon successive reduction, with the formal Ru oxidation state from +2 to -4. In the case of highly reduced complexes, proper representation of the electrochromic reaction is actually the reduction of the hgand, not that of the metal center. 

Cationic ferrocene complexes with one, two, and four cationic [B(R)bpy] (bpy = 2,2,-bipyridine) acceptors such as 66 show absorption at Amax = 496-540 nm with the contribution of charge transfer between the ferrocene unit and the B(R)bpy substituent(s) (165). This is confirmed by the EPR spectrum of the monoreduced neutral species, which features a line shape indicating a considerable admixture of the ligand and metal orbitals. Preparation and physical properties of the related polymer, 67, have also been reported (166). 

There has been considerable interest in the study of multinuclear metal complexes with bridging sulfide ligands.381 The first examples of triangulo palladium(II) are the complexes containing substituted 2,2 -bipyridine and triply bridging sulfide ligands, namely [Pd3(diimine)3(M3-S)2][C104]2382... 

Triply bridging carbonates between three zinc centers have been identified in nine different X-ray structures deposited in the CSD 458,461,465-467 For example, a binuclear ft-OH zinc complex with a tetradentate /V-donor ligand absorbs atmospheric carbon dioxide to a triply bridged carbonate.468 Examples are also known where the metal atoms are in varying coordination environments. The complex cation [Zn3(bipyridine)6(/U3-C03)(H20)2]4+ contains one penta- and two hexacoordinate zinc centers.469 A tetrapodal compartmental ligand forms a tetrameric complex with zinc that contains the carbonate bridging between three of the four zinc centers.470... 

Triruthenium Complexes with Ortho-Metallated 2,2 -bipyridine or 1,10-Phenanthroline... 

These results suggest that the critical factor in the substrate-mediated intermolecular interactions which occur within the close-packed DHT layer is the inherent strong reactivity of the diphenolic moiety with the Pt surface. The interaction of adsorbates with each other through the mediation of the substrate is of fundamental importance in surface science. The theoretical treatment, however, involves complicated many-body potentials which are presently not well-understood (2.). It is instructive to view the present case of Pt-substrate-mediated DHT-DHT interactions in terms of mixed-valence metal complexes (2A) For example, in the binuclear mixed-valence complex, (NH3)5RU(11)-bpy-Ru(111) (NH 3)5 (where bpy is 4,4 -bipyridine), the two metal centers are still able to interact with each other via the delocalized electrons within the bpy ligand. The interaction between the Ru(II) and Ru(III) ions in this mixed-valence complex is therefore ligand-mediated. The Ru(II)-Ru(III) coupling can be written schematically as ... 

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