Proton-induced generation of remote N-heterocyclic carbene-Ru complexes

Takashi Fukushima; Ryoichi Fukuda; Katsuaki Kobayashi; Giovanni F. Caramori; Gernot Frenking; Masahiro Ehara; Koji Tanaka

doi:10.1002/chem.201404932

Proton-induced generation of remote N-heterocyclic carbene-Ru complexes

Takashi Fukushima, Ryoichi Fukuda, Katsuaki Kobayashi, Giovanni F. Caramori, Gernot Frenking, Masahiro Ehara, Koji Tanaka

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

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.

Original language	English
Pages (from-to)	106-110
Number of pages	5
Journal	Chemistry - A European Journal
Volume	21
Issue number	1
DOIs	https://doi.org/10.1002/chem.201404932
State	Published - 2 Jan 2015
Externally published	Yes

Keywords

Bond theory
Carbene ligands
Density functional calculations
Electronic structure
Ruthenium

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title = "Proton-induced generation of remote N-heterocyclic carbene-Ru complexes",

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.",

keywords = "Bond theory, Carbene ligands, Density functional calculations, Electronic structure, Ruthenium",

author = "Takashi Fukushima and Ryoichi Fukuda and Katsuaki Kobayashi and Caramori, {Giovanni F.} and Gernot Frenking and Masahiro Ehara and Koji Tanaka",

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year = "2015",

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doi = "10.1002/chem.201404932",

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AU - Fukushima, Takashi

AU - Fukuda, Ryoichi

AU - Kobayashi, Katsuaki

AU - Caramori, Giovanni F.

AU - Frenking, Gernot

AU - Ehara, Masahiro

AU - Tanaka, Koji

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

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DO - 10.1002/chem.201404932

M3 - 文章

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JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 1

ER -

Proton-induced generation of remote N-heterocyclic carbene-Ru complexes

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Keywords

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