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trans‐ (Cl)‐[Ru(5,5′‐diamide‐2,2′‐bipyridine)(CO) 2 Cl 2 ]: Synthesis, Structure, and Photocatalytic CO 2 Reduction Activity
Author(s) -
Kuramochi Yusuke,
Fukaya Kyohei,
Yoshida Makoto,
Ishida Hitoshi
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201500782
Subject(s) - ruthenium , amide , chemistry , homo/lumo , catalysis , medicinal chemistry , photosensitizer , bipyridine , stereochemistry , ligand (biochemistry) , photochemistry , crystallography , molecule , crystal structure , organic chemistry , biochemistry , receptor
A series of trans‐ (Cl)‐[Ru(L)(CO) 2 Cl 2 ]‐type complexes, in which the ligands L are 2,2′‐bipyridyl derivatives with amide groups at the 5,5′‐positions, are synthesized. The C‐connected amide group bound to the bipyridyl ligand through the carbonyl carbon atom is twisted with respect to the bipyridyl plane, whereas the N‐connected amide group is in the plane. DFT calculations reveal that the twisted structure of the C‐connected amide group raises the level of the LUMO, which results in a negative shift of the first reduction potential ( E p ) of the ruthenium complex. The catalytic abilities for CO 2 reduction are evaluated in photoreactions ( λ >400 nm) with the ruthenium complexes (the catalyst), [Ru(bpy) 3 ] 2+ (bpy=2,2′‐bipyridine; the photosensitizer), and 1‐benzyl‐1,4‐dihydronicotinamide (the electron donor) in CO 2 ‐saturated N,N ‐dimethylacetamide/water. The logarithm of the turnover frequency increases by shifting E p a negative value until it reaches the reduction potential of the photosensitizer.