TY - JOUR
T1 - Proton-induced generation of remote N-heterocyclic carbene-Ru complexes
AU - Fukushima, Takashi
AU - Fukuda, Ryoichi
AU - Kobayashi, Katsuaki
AU - Caramori, Giovanni F.
AU - Frenking, Gernot
AU - Ehara, Masahiro
AU - Tanaka, Koji
N1 - Publisher Copyright:
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2015/1/2
Y1 - 2015/1/2
N2 - The proton-induced Ru-C bond variation, which was previously found to be relevant in the water oxidation, has been investigated by using cyclometalated ruthenium complexes with three phenanthroline (phen) isomers. The designed complexes, [Ru(bpy)2(1,5-phen)]+([2]+), [Ru(bpy)2(1,6-phen)]+ ([3]+), and [Ru(bpy)2(1,7-phen)]+ ([4]+) were newly synthesized and their structural and electronic properties were analyzed by various spectroscopy and theoretical protocols. Protonation of [4]+triggered profound electronic structural change to form remote N-heterocyclic carbene (rNHC), whereas protonation of [2]+ and [3]+ did not affect their structures. It was found that changes in the electronic structure of phen beyond classical resonance forms control the rNHC behavior. The present study provides new insights into the ligand design of related ruthenium catalysts.
AB - The proton-induced Ru-C bond variation, which was previously found to be relevant in the water oxidation, has been investigated by using cyclometalated ruthenium complexes with three phenanthroline (phen) isomers. The designed complexes, [Ru(bpy)2(1,5-phen)]+([2]+), [Ru(bpy)2(1,6-phen)]+ ([3]+), and [Ru(bpy)2(1,7-phen)]+ ([4]+) were newly synthesized and their structural and electronic properties were analyzed by various spectroscopy and theoretical protocols. Protonation of [4]+triggered profound electronic structural change to form remote N-heterocyclic carbene (rNHC), whereas protonation of [2]+ and [3]+ did not affect their structures. It was found that changes in the electronic structure of phen beyond classical resonance forms control the rNHC behavior. The present study provides new insights into the ligand design of related ruthenium catalysts.
KW - Bond theory
KW - Carbene ligands
KW - Density functional calculations
KW - Electronic structure
KW - Ruthenium
UR - http://www.scopus.com/inward/record.url?scp=84920363541&partnerID=8YFLogxK
U2 - 10.1002/chem.201404932
DO - 10.1002/chem.201404932
M3 - 文章
AN - SCOPUS:84920363541
SN - 0947-6539
VL - 21
SP - 106
EP - 110
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 1
ER -