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Updated: Apr 21, 2026

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
Published on: November 29, 2018
Proton-induced generation of remote N-heterocyclic carbene-Ru complexes
Takashi Fukushima1, Ryoichi Fukuda, Katsuaki Kobayashi
1Institute for Integrated Cell-Material Science, Kyoto University, Room 507, Advanced Chemical Technology Center in Kyoto, 105 Jibu-cho, Fushimi-ku, Kyoto 612-8374 (Japan).
Abstract:
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.
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