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Proton‐Induced Generation of Remote N‐Heterocyclic Carbene–Ru Complexes
Author(s) -
Fukushima Takashi,
Fukuda Ryoichi,
Kobayashi Katsuaki,
Caramori Giovanni F.,
Frenking Gernot,
Ehara Masahiro,
Tanaka Koji
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.201404932
Subject(s) - ruthenium , carbene , protonation , chemistry , proton , ligand (biochemistry) , photochemistry , catalysis , phenanthroline , electronic structure , spectroscopy , resonance (particle physics) , crystallography , stereochemistry , computational chemistry , ion , organic chemistry , biochemistry , physics , receptor , particle physics , quantum mechanics
The proton‐induced RuC 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.