Synthesis and Characterization of an Azido-Bridged Dinuclear Ruthenium(II) Polypyridylamine Complex Forming a Mixed-Valence State

被引：14

作者：

Makino, Misaki ^{[1
]}

Ishizuka, Tomoya ^{[1
]}

Ohzu, Shingo ^{[1
]}

Hua, Jiang ^{[1
]}

Kotani, Hiroaki ^{[1
]}

Kojima, Takahiko ^{[1
]}

机构：

[1] Univ Tsukuba, Grad Sch Pure & Appl Sci, Dept Chem, Tsukuba, Ibaraki 3058571, Japan

来源：

INORGANIC CHEMISTRY | 2013年 / 52卷 / 09期

关键词：

ELECTRON-TRANSFER; MAGNETIC-PROPERTIES; CRYSTAL-STRUCTURE; SPECTROSCOPIC PROPERTIES; NICKEL(II) COMPLEXES; PYRIDYLAMINE LIGANDS; BINUCLEAR COMPLEXES; IRON; COMMUNICATION; TRANSITION;

D O I：

10.1021/ic400412f

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

We have synthesized a mononuclear ruthenium(II) azido complex (1) and a dinuclear ruthenium(II) mu-azido complex (2) having N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine (N4Py) as a pentadentate ancillary ligand. In the crystal structure of 2, intramolecular pi-pi stacking was found between the pyridine rings of the two different N4Py ligands, contributing to stabilize the dinuclear mu-azido structure. pi donation from the HOMO pi* orbital of the mu-azido ligand to the Ru-N(pyr) bond increases the bond order between the terminal and central N atoms in the mu-azido ligand to strengthen the N-N bonds of the mu-azido ligand. The mu-azido complex 2 was revealed to exhibit a stepwise oxidation behavior in CH3CN to afford a Ru-II-mu-azido-Ru-III mixed-valence (MV) state upon one-electron oxidation. The MV state of one-electron-oxidized 2 was categorized in the Robin-Day class II with the electronic coupling constant (H-ab) of 570 cm(-1).

引用

页码：5507 / 5514

页数：8

共 50 条

[1] Mixed-valence properties of an acetate-bridged dinuclear ruthenium (II,III) complex
Lomoth, R
Magnuson, A
Xu, YH
Sun, LC
[J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2003, 107 (22): : 4373 - 4380
[2] Mixed-valence properties of a dinuclear ruthenium complex bridged by bis(phenylcyanamido)tetrazine
Habibagahi, Fatemeh
Crutchley, Robert J.
[J]. CANADIAN JOURNAL OF CHEMISTRY, 2014, 92 (11) : 1081 - 1085
[3] Synthesis, electrochemistry and mixed-valence state of dinuclear tris(acetylacetonato)ruthenium(III) complexes bridged by sulfur atoms at the γ-position of acetylacetonate
Endo, A
Sibasaki, M
Nagao, H
Shimizu, K
[J]. INORGANICA CHIMICA ACTA, 2004, 357 (12) : 3443 - 3450
[4] Possibility of Dielectric Material: Magnetic Resonance Study of Oxo-Bridged Dinuclear Ruthenium Mixed-Valence Complex
Nakamura, Toshikazu
Asada, Mizue
Yoshida, Masaki
Kondo, Mio
Masaoka, Shigeyuki
[J]. CHEMISTRYSELECT, 2018, 3 (37): : 10526 - 10531
[5] MIXED-VALENCE PROPERTIES OF A PYRAZINE BRIDGED RUTHENIUM-IRON COMPLEX
TOMA, HE
SANTOS, PS
[J]. CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1977, 55 (20): : 3549 - 3553
[6] PREPARATION AND CHARACTERIZATION OF A MIXED-VALENCE CYANOBRIDGED COBALT(III)RUTHENIUM(II) COMPLEX
BAGGER, S
STOLTZE, P
[J]. ACTA CHEMICA SCANDINAVICA SERIES A-PHYSICAL AND INORGANIC CHEMISTRY, 1981, 35 (07): : 509 - 512
[7] CHARACTERIZATION OF BINUCLEAR MIXED-VALENCE RUTHENIUM COMPLEXES BRIDGED BY A TETRADENTATE LIGAND
SEDNEY, D
LUDI, A
[J]. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 1981, 181 (MAR): : 186 - INOR
[8] CHARACTERIZATION OF A MIXED-VALENCE CYANO-BRIDGED COBALT(III)IRON(II) COMPLEX
BAGGER, S
STOLTZE, P
[J]. ACTA CHEMICA SCANDINAVICA SERIES A-PHYSICAL AND INORGANIC CHEMISTRY, 1983, 37 (03): : 247 - 250
[9] Dinuclear alkoxide-bridged ruthenium(II) complexes with Class III mixed-valence states: A structural and spectroelectrochemical study
Bardwell, DA
Horsburgh, L
Jeffery, JC
Joulie, LF
Ward, MD
Webster, I
Yellowlees, LJ
[J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1996, (12): : 2527 - 2531
[10] Triply bridged dinuclear ruthenium complexes bearing alkylbis(2-pyridylmethyl)amine in the mixed-valence state of Ru(II)-Ru(III)
Misawa-Suzuki, T.
Matsuya, K.
Watanabe, T.
Nagao, H.
[J]. DALTON TRANSACTIONS, 2018, 47 (45) : 16182 - 16189

← 1 2 3 4 5 →