Oxidation and deprotonation of a ruthenium(II) complex with quinoline-2-carbaldehyde (pyridine-2-carbonyl)hydrazone and formation of hydrazonato-bridged heterodimetallic complexes

Asami Mori, Takayoshi Suzuki, Yukinari Sunatsuki, Masaaki Kojima, Kiyohiko Nakajima

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Abstract

Reactions of a ruthenium(II) complex containing quinoline-2-carbaldehyde (pyridine-2-carbonyl)hydrazone (HL), trans(P,P)-[RuCl2(PPh3)2(HL)] (1), and 3d-metal(II) chlorides resulted in heterodimetallic complexes, [RuCl2(PPh3)2-(μ-L)MCl2] (2M, M = Mn, Fe, Co, Ni, Cu, and Zn), in which the deprotonated hydrazonate (L-) bridged two metal ions in the μ-1(Ru)κ2N,O:2(M)κ3N′,N″,N⌄ mode. The coordination bond lengths around the Ru and M centers suggested that the oxidation states in the complexes 2M could be assigned as RuIII and MII; this was also supported by magnetic, electrochemical, and spectroscopic measurements. In addition, oxidation of complex 1 by (NH4)2[Ce(NO3)6] gave the corresponding mononuclear RuIII complex with the deprotonated hydrazonate, trans(P,P)-[RuCl2(PPh3)2(L)] (3). It is suggested that oxidation of the Ru center lead to the concerted deprotonation from the hydrazone ligand. Addition of excess HClO4 to complex 3 gave a doubly protonated RuIII complex, 4(ClO4)2; in this complex the hydrazonate moiety was not protonated, but both the quinolyl and pyridyl N atoms were protonated. Complexes 3 and 42+ could be interconverted by the addition of acid or base without changing the oxidation state of the Ru center.

Original languageEnglish
Pages (from-to)480-489
Number of pages10
JournalBulletin of the Chemical Society of Japan
Volume88
Issue number3
DOIs
Publication statusPublished - 2015

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Hydrazones
Deprotonation
Ruthenium
Oxidation
Bond length
Metal ions
Chlorides
Metals
Ligands
Atoms
Acids
pyridine-2-carbaldehyde
quinoline

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{82e325fd379e4770b4858dc78680599e,
title = "Oxidation and deprotonation of a ruthenium(II) complex with quinoline-2-carbaldehyde (pyridine-2-carbonyl)hydrazone and formation of hydrazonato-bridged heterodimetallic complexes",
abstract = "Reactions of a ruthenium(II) complex containing quinoline-2-carbaldehyde (pyridine-2-carbonyl)hydrazone (HL), trans(P,P)-[RuCl2(PPh3)2(HL)] (1), and 3d-metal(II) chlorides resulted in heterodimetallic complexes, [RuCl2(PPh3)2-(μ-L)MCl2] (2M, M = Mn, Fe, Co, Ni, Cu, and Zn), in which the deprotonated hydrazonate (L-) bridged two metal ions in the μ-1(Ru)κ2N,O:2(M)κ3N′,N″,N⌄ mode. The coordination bond lengths around the Ru and M centers suggested that the oxidation states in the complexes 2M could be assigned as RuIII and MII; this was also supported by magnetic, electrochemical, and spectroscopic measurements. In addition, oxidation of complex 1 by (NH4)2[Ce(NO3)6] gave the corresponding mononuclear RuIII complex with the deprotonated hydrazonate, trans(P,P)-[RuCl2(PPh3)2(L)] (3). It is suggested that oxidation of the Ru center lead to the concerted deprotonation from the hydrazone ligand. Addition of excess HClO4 to complex 3 gave a doubly protonated RuIII complex, 4(ClO4)2; in this complex the hydrazonate moiety was not protonated, but both the quinolyl and pyridyl N atoms were protonated. Complexes 3 and 42+ could be interconverted by the addition of acid or base without changing the oxidation state of the Ru center.",
author = "Asami Mori and Takayoshi Suzuki and Yukinari Sunatsuki and Masaaki Kojima and Kiyohiko Nakajima",
year = "2015",
doi = "10.1246/bcsj.20140381",
language = "English",
volume = "88",
pages = "480--489",
journal = "Bulletin of the Chemical Society of Japan",
issn = "0009-2673",
publisher = "Chemical Society of Japan",
number = "3",

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TY - JOUR

T1 - Oxidation and deprotonation of a ruthenium(II) complex with quinoline-2-carbaldehyde (pyridine-2-carbonyl)hydrazone and formation of hydrazonato-bridged heterodimetallic complexes

AU - Mori, Asami

AU - Suzuki, Takayoshi

AU - Sunatsuki, Yukinari

AU - Kojima, Masaaki

AU - Nakajima, Kiyohiko

PY - 2015

Y1 - 2015

N2 - Reactions of a ruthenium(II) complex containing quinoline-2-carbaldehyde (pyridine-2-carbonyl)hydrazone (HL), trans(P,P)-[RuCl2(PPh3)2(HL)] (1), and 3d-metal(II) chlorides resulted in heterodimetallic complexes, [RuCl2(PPh3)2-(μ-L)MCl2] (2M, M = Mn, Fe, Co, Ni, Cu, and Zn), in which the deprotonated hydrazonate (L-) bridged two metal ions in the μ-1(Ru)κ2N,O:2(M)κ3N′,N″,N⌄ mode. The coordination bond lengths around the Ru and M centers suggested that the oxidation states in the complexes 2M could be assigned as RuIII and MII; this was also supported by magnetic, electrochemical, and spectroscopic measurements. In addition, oxidation of complex 1 by (NH4)2[Ce(NO3)6] gave the corresponding mononuclear RuIII complex with the deprotonated hydrazonate, trans(P,P)-[RuCl2(PPh3)2(L)] (3). It is suggested that oxidation of the Ru center lead to the concerted deprotonation from the hydrazone ligand. Addition of excess HClO4 to complex 3 gave a doubly protonated RuIII complex, 4(ClO4)2; in this complex the hydrazonate moiety was not protonated, but both the quinolyl and pyridyl N atoms were protonated. Complexes 3 and 42+ could be interconverted by the addition of acid or base without changing the oxidation state of the Ru center.

AB - Reactions of a ruthenium(II) complex containing quinoline-2-carbaldehyde (pyridine-2-carbonyl)hydrazone (HL), trans(P,P)-[RuCl2(PPh3)2(HL)] (1), and 3d-metal(II) chlorides resulted in heterodimetallic complexes, [RuCl2(PPh3)2-(μ-L)MCl2] (2M, M = Mn, Fe, Co, Ni, Cu, and Zn), in which the deprotonated hydrazonate (L-) bridged two metal ions in the μ-1(Ru)κ2N,O:2(M)κ3N′,N″,N⌄ mode. The coordination bond lengths around the Ru and M centers suggested that the oxidation states in the complexes 2M could be assigned as RuIII and MII; this was also supported by magnetic, electrochemical, and spectroscopic measurements. In addition, oxidation of complex 1 by (NH4)2[Ce(NO3)6] gave the corresponding mononuclear RuIII complex with the deprotonated hydrazonate, trans(P,P)-[RuCl2(PPh3)2(L)] (3). It is suggested that oxidation of the Ru center lead to the concerted deprotonation from the hydrazone ligand. Addition of excess HClO4 to complex 3 gave a doubly protonated RuIII complex, 4(ClO4)2; in this complex the hydrazonate moiety was not protonated, but both the quinolyl and pyridyl N atoms were protonated. Complexes 3 and 42+ could be interconverted by the addition of acid or base without changing the oxidation state of the Ru center.

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U2 - 10.1246/bcsj.20140381

DO - 10.1246/bcsj.20140381

M3 - Article

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VL - 88

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EP - 489

JO - Bulletin of the Chemical Society of Japan

JF - Bulletin of the Chemical Society of Japan

SN - 0009-2673

IS - 3

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