Tuning of Metal–Metal Interactions in Mixed-Valence States of Cyclometalated Dinuclear Ruthenium and Osmium Complexes Bearing Tetrapyridylpyrazine or -benzene

2014 ◽  
Vol 33 (18) ◽  
pp. 4893-4904 ◽  
Author(s):  
Takumi Nagashima ◽  
Takuya Nakabayashi ◽  
Takashi Suzuki ◽  
Katsuhiko Kanaizuka ◽  
Hiroaki Ozawa ◽  
...  
Keyword(s):  
Mixed Valence ◽  
Metal Interactions ◽  
Valence States ◽  
Metal Metal ◽  
Dinuclear Ruthenium ◽  
Osmium Complexes

Proton-induced switching of metal-metal interactions in dinuclear ruthenium and osmium complexes bridged by 2,2'-bis(2-pyridyl)bibenzimidazole

1991 ◽  
Vol 30 (20) ◽  
pp. 3843-3849 ◽  
Author(s):  
Masaaki. Haga ◽  
Tomoaki. Ano ◽  
Kenji. Kano ◽  
Shinichi. Yamabe
Keyword(s):  
Metal Interactions ◽  
Metal Metal ◽  
Dinuclear Ruthenium ◽  
Osmium Complexes

Density Functional Investigation of Metal−Metal Interactions in Mixed-Valence d2d3(Cr, Mo, W) and d3d4(Mn, Tc, Re) Face-Shared [M2Cl9]2-Systems

2004 ◽  
Vol 43 (21) ◽  
pp. 6734-6744 ◽  
Author(s):  
Germán Cavigliasso ◽  
Peter Comba ◽  
Robert Stranger
Keyword(s):  
Density Functional ◽  
Mixed Valence ◽  
Metal Interactions ◽  
Metal Metal ◽  
Functional Investigation

Intervalence transfer in a new benzotriazolate bridged ruthenium-iron complex

2001 ◽  
Vol 79 (2) ◽  
pp. 145-156
Author(s):  
Reginaldo C Rocha ◽  
Henrique E Toma
Keyword(s):  
Near Infrared ◽  
Mixed Valence ◽  
Differential Pulse ◽  
Iron Complex ◽  
Electronic Coupling ◽  
Near Ir ◽  
Metal Metal ◽  
Dinuclear Ruthenium ◽  
Pulse Voltammetry ◽  
Transfer Properties

The unsymmetrical dinuclear ruthenium–iron complexes [(NH3)5Ru–bta–Fe(CN)5]n (where bta = benzotriazolate; n = –2, –1, 0) were prepared as solid sodium salts from [RuII(NH3)5(bta)]+ or [RuIII(NH3)5(bta)]2+ and [FeII(CN)5(H2O)]3– and characterized in aqueous solution by means of electrochemical and spectroelectrochemical methods. UV-vis, near-infrared, IR, and cyclic and differential pulse voltammetry data suggest that the related mixed valent species belong to a valence trapped formulation, featuring localized Ru(III) and Fe(II) oxidation states. In spite of the class II categorization in the Robin and Day scheme, this system shows a remarkable metal–metal electronic coupling, as deduced from an intense, low-energy, and very broad intervalence band in the near-IR region. In addition, the mixed valence state displays enhanced stabilization in relation to the isovalent state. The intervalence transfer properties are discussed on the basis of Hush's theory.Key words: ammineruthenium complexes, cyanoiron complexes, mixed valence, intervalence, benzotriazole, benzotriazolate.

Highly coupled mixed-valence dinuclear ruthenium and osmium complexes with a bis-cyclometalating terpyridine analog as bridging ligand

1993 ◽  
Vol 32 (21) ◽  
pp. 4539-4543 ◽  
Author(s):  
Marc Beley ◽  
Jean Paul Collin ◽  
Jean Pierre Sauvage
Keyword(s):  
Mixed Valence ◽  
Bridging Ligand ◽  
Dinuclear Ruthenium ◽  
Osmium Complexes

Linear Chain Bis(α,β-dionedioximato)metal Compounds of the Nickel Triad: Solid State Design by Molecular Engineering

1977 ◽  
Vol 32 (5) ◽  
pp. 516-527 ◽  
Author(s):  
H. Endres ◽  
H. J. Keller ◽  
R. Lehmann ◽  
A. Poveda ◽  
H. H. Rupp ◽  
...  
Keyword(s):  
Solid State ◽  
Linear Chain ◽  
Mixed Valence ◽  
Structural Data ◽  
Molecular Engineering ◽  
Complex Molecules ◽  
Metal Compounds ◽  
Metal Interactions ◽  
Wide Range ◽  
Metal Metal

Chemical and structural data of numerous bis(α,β-dionedioximato)metal(II) compounds are summarized. All of them crystallize in columns but principally two different kinds of molecular arrangements occur in the solids. In one phase the molecular planes are inclined to the direction of the linear metal chains with an angle different from 90°. This allows only indirect interactions between the metal ions via the ligand. (“M—L—M” stacking.) The other modification consists of molecules with their planes perpendicular to the M—M-chains. This form allows direct metal-metal contacts (“M—M” modification). Depending on a few molecular parameters a “M—L—M” or a “M—M” stacking is obtained upon crystallization. Since for those compounds which could be isolated in both modifications the M—L—M form has the higher density it is concluded that only stronger M—M interactions stabilize the less dense M—M forms.A wide range of metal-metal separations with a lower limit of 3.15 Å in mixed valence systems are found in different “M—M” compounds. In any case the intrachain metal-metal distances are reduced considerably upon oxidation of the bivalent complex molecules. The influence of “electronic” and “sterical” parameters of the complex molecules on the intermolecular metal interactions and on the type of columns in the solid state is discussed.

scholarly journals Dinuclear ruthenium complexes containing a new ditopic phthalazin-bis(triazole) ligand that promotes metal–metal interactions

2014 ◽  
Vol 38 (5) ◽  
pp. 1980-1987 ◽  
Author(s):  
Joan Aguiló ◽  
Atena Naeimi ◽  
Roger Bofill ◽  
Helge Mueller-Bunz ◽  
Antoni Llobet ◽  
...  
Keyword(s):  
Ruthenium Complexes ◽  
Metal Interactions ◽  
Metal Metal ◽  
Triazole Ligand ◽  
Dinuclear Ruthenium ◽  
Dinuclear Ruthenium Complexes

scholarly journals Metal–metal interactions in dinuclear ruthenium complexes containing bridging 4,5-di(2-pyridyl)imidazolates and related ligands

2006 ◽  
pp. 1954-1962 ◽  
Author(s):  
Jonathan W. Slater ◽  
Deanna M. D'Alessandro ◽  
F. Richard Keene ◽  
Peter J. Steel
Keyword(s):  
Ruthenium Complexes ◽  
Metal Interactions ◽  
Metal Metal ◽  
Dinuclear Ruthenium ◽  
Dinuclear Ruthenium Complexes
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