A pentaammineruthenium mixed-valence complex with 1,4-dicyanamido-2,3,5,6-tetrachlorobenzene dianion as bridging ligand: symmetry-attenuated electronic coupling between redox sites

1990 ◽  
Vol 29 (19) ◽  
pp. 3641-3644 ◽  
Author(s):  
Manuel A. S. Aquino ◽  
Ann E. Bostock ◽  
Robert J. Crutchley
Keyword(s):  
Mixed Valence ◽  
Electronic Coupling ◽  
Bridging Ligand ◽  
Redox Sites ◽  
Mixed Valence Complex

Driving the Localized-to-Delocalized Transition in Unsymmetrical Dinuclear Ruthenium Mixed-Valence Complexes

2005 ◽  
Vol 58 (11) ◽  
pp. 767 ◽  
Author(s):  
Deanna M. D'Alessandro ◽  
F. Richard Keene
Keyword(s):  
Electronic State ◽  
Ground State ◽  
Mixed Valence ◽  
Electronic Coupling ◽  
Classical Analysis ◽  
Bridging Ligand ◽  
Dinuclear Ruthenium ◽  
State Analysis

The degree of delocalization in the symmetrical complexes [{Ru(bpy)2}2(μ-dpb′)]5+ and [{Ru(bpy)2}2(μ-dpb)]5+ (dpb = 2,3-bis(2-pyridyl)-1,4-benzoquinoxaline; dpb′ = dipyrido(2,3-a;3′,2′-c)benzophenazine; bpy = 2,2′-bipyridine) is diminished by the substitution of the terminal bpy ligands at one end of the complex. The results of a classical analysis for the diastereoisomeric forms of the series of complexes [{Ru(bpy)2}(μ-BL){Ru(pp)2}]5+ (pp = bpy, Me2bpy (4,4′-dimethyl-2,2′-bipyridine), Me4bpy (4,4′,5,5′-tetramethyl-2,2′-bipyridine)) indicate that a greater degree of ground-state delocalization exists in the complexes incorporating the bridging ligand dpb′ compared with the dpb analogue. A two-state analysis in which ΔE 0 (the redox asymmetry) is varied at constant H ab (the electronic coupling) and λ (the reorganizational energy) does not adequately describe the properties of the systems due to the importance of a third electronic state corresponding to the bridging ligand.

Strong Metal-Metal Coupling in a Dinuclear Terpyridinebipyridineruthenium Mixed-Valence Complex Incorporating the Bridging Ligand 1,4-Dicyanamidobenzene Dianion

1995 ◽  
Vol 34 (18) ◽  
pp. 4600-4604 ◽  
Author(s):  
Ali R. Rezvani ◽  
Christopher E. B. Evans ◽  
Robert J. Crutchley
Keyword(s):  
Mixed Valence ◽  
Bridging Ligand ◽  
Metal Metal ◽  
Mixed Valence Complex

Mixed valence complexes involving MM quadruple bonds (M=Mo or W)

2007 ◽  
Vol 366 (1862) ◽  
pp. 101-112 ◽  
Author(s):  
Malcolm H Chisholm
Keyword(s):  
Mixed Valence ◽  
Electronic Coupling ◽  
Organic Radical ◽  
Radical Anions ◽  
Class Iii ◽  
Mixed Valency ◽  
Bridging Ligand ◽  
Quadruple Bond ◽  
Redox Active ◽  
Quadruple Bonds

The MM quadruple bond of configuration MM σ 2 π 4 δ 2 is redox active and in many ways ideally suited for studies of mixed valency when two or more such centres are linked by a bridging ligand. In this account, the mechanism of electronic coupling is examined for complexes of the type [L 3 M 2 bridgeM 2 L 3 ] 0/+ where L, a pivalate; bridge, a dicarboxylate or related ligand and M, Mo or W. The represented examples allow us to probe electronic factors close to the class II/III border and readily distinguish between electron and hole transfer in the superexchange mechanism. The potential for mixed valence organic radical anions mediated by the M 2 centre is also raised and one specific example of class III behaviour is described.

A Donor−Acceptor−Donor Bridging Ligand in a Class III Mixed-Valence Complex

2001 ◽  
Vol 40 (6) ◽  
pp. 1189-1195 ◽  
Author(s):  
Peter J. Mosher ◽  
Glenn P. A. Yap ◽  
Robert J. Crutchley
Keyword(s):  
Mixed Valence ◽  
Class Iii ◽  
Bridging Ligand ◽  
Donor Acceptor ◽  
Mixed Valence Complex

The influence of cis/trans isomerism on the physical properties of a cyano-bridged dinuclear mixed valence complex

2002 ◽  
pp. 1435 ◽  
Author(s):  
Paul V. Bernhardt ◽  
Brendan P. Macpherson ◽  
Manuel Martinez
Keyword(s):  
Physical Properties ◽  
Mixed Valence ◽  
Mixed Valence Complex

Design, synthesis and physico-chemical studies of a Co(II)/Co(III) mixed-valence complex: An experimental and DFT approach.

2021 ◽  
pp. 130384
Author(s):  
Intissar Hamdi ◽  
Noureddine Mhadhbi ◽  
Noureddine Issaoui ◽  
Andreas Roodt ◽  
Mark M. Turnbull ◽  
...  
Keyword(s):  
Mixed Valence ◽  
Design Synthesis ◽  
Physico Chemical ◽  
Chemical Studies ◽  
Mixed Valence Complex
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