Abstract
The reactivities of transition metal coordination compounds are often controlled by the environment around the coordination sphere. For ruthenium(II) complexes, differences in polypyridyl supporting ligands affect some types of reactivity despite identical coordination geometries. To evaluate the synergistic effects of (i) the supporting ligands, and (ii) the coordination geometry, a series of dicarbonyl–ruthenium(II) complexes that contain both asymmetric and symmetric bidentate polypyridyl ligands were synthesized. Molecular structures of the complexes were determined by X-ray crystallography to distinguish their steric configuration. Structural, computational, and electrochemical analysis revealed some differences between the isomers. Photo- and thermal reactions indicated that the reactivities of the complexes were significantly affected by both their structures and the ligands involved.
Highlights
Polypyridines with multiple covalently bonded pyridine groups exhibit unique photophysical and redox properties [1,2]
Bipyridine analogues play an important role in the formation of various transition metal complexes as bidentate ligands with two nitrogen donor atoms [3]
A variety of studies that imparted selectivity to various reactions by strictly controlling the coordination sphere have been reported for many ruthenium complexes
Summary
Polypyridines with multiple covalently bonded pyridine groups exhibit unique photophysical and redox properties [1,2]. Various molecular structures can be readily designed for a ruthenium center because ruthenium can take various oxidation states and can interact with the ligand. These structures include examples where differences in the coordination geometry dramatically changed both the electrical and photochemical properties of the complex, and its catalysis for chemical reactions [14,15,16]. Many examples of the relationship between the supporting bipyridine ligands and the reactivity of metal complexes are known. The relationship between the number of heteroatoms involved in the supporting ligand and the reactivity of the complex has been reported in a ruthenium complex containing bipyridine analogues [17]
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