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
N1 - Publisher Copyright:
© 2015 The Chemical Society of Japan.
Copyright:
Copyright 2015 Elsevier B.V., All rights reserved.
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
AN - SCOPUS:84925397762
SN - 0009-2673
VL - 88
SP - 480
EP - 489
JO - Bulletin of the Chemical Society of Japan
JF - Bulletin of the Chemical Society of Japan
IS - 3
ER -