Synthesis, Characterization, and Substituent Effects of Binuclear Ruthenium Vinyl Complexes [RuCl(CO)(PMe3)3]2(μ-CH═CH−Ar−CH═CH)

Wu, Xiang; Jin, Shan; Liang, Jin; Li, Zi Yong; Yu, Guang‐Ao; Liu, Sheng Hua

doi:10.1021/om900018y

Cited by 55 publications

(42 citation statements)

References 146 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Our previous study on [RuCl (CO)(PMe 3 ) 3 ] 2 (CH=CHC 6 H 4 CH=CH) compounds revealed that each methyl substituent increases DE p by about 4mVt hrough modification of 1,4-diethenylphenylene bridging ligand. [63,64] Thus, from the potentials hift induced only by the torsion angle of the biphenyl core, one can estimate that the DE p values should be about 181, 166, 127, 68, and 65 mV for complexes 4a-e,respectively.According to theory,the orbitaloverlap of adjacent p systems correlates linearly with the cos f value, and the electron transmission is proportionalt o cos 2 f. [65] As shown in Figure 3, the potential differences between the first and second redox peaks DE p exhibit am oderately good linear correlation with cos 2 f (R 2 = 0.973). An intercept of about 64 mV was obtained for the situation in which very little or no communication exists between the two ruthenium units (f= 908).…”

Section: Electrochemistrymentioning

confidence: 99%

Conformational Tuning of the Intramolecular Electronic Coupling in Molecular‐Wire Biruthenium Complexes Bridged by Biphenyl Derivatives

Kong

Xue

Jang

et al. 2015

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

The synthesis and characterization of a series of biphenyl-derived binuclear ruthenium complexes with terminal {RuCl(CO)(PMe3)3} moieties and different structural arrangements of the phenyl rings are reported. Electrochemical studies revealed that the two metal centers of the binuclear ruthenium complexes interact with each other through the biphenyl bridge, and the redox splittings ΔE1/2 show a strong linear correlation with cos(2) ϕ, where ϕ is the torsion angle between the two phenyl rings. A combination of electrochemical, UV/Vis/NIR, and in situ IR differential spectroelectrochemical analysis clearly showed that: 1) the intramolecular electronic couplings in the binuclear ruthenium complexes could be modulated by changing ϕ; 2) the electronic ground state of the mixed-valent cations changes from delocalized to localized through the biphenyl bridge with increasing torsion angle ϕ, that is, the redox processes of these complexes change from significant involvement of the bridging ligand to an oxidation behavior with less participation of the bridge.

show abstract

Section: Electrochemistrymentioning

confidence: 99%

Conformational Tuning of the Intramolecular Electronic Coupling in Molecular‐Wire Biruthenium Complexes Bridged by Biphenyl Derivatives

Kong

Xue

Jang

et al. 2015

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

show abstract

“…ν(CO) Values (cm −1 ) for the Complexes Ru(CO)(L)(P i Pr 3 ) 2 (CHCHC6 H 4 R-4) and Their Radical Cations…”

mentioning

confidence: 99%

Ruthenium Styryl Complexes with Ligands Derived from 2-Hydroxy- and 2-Mercaptopyridine and 2-Hydroxy- and 2-Mercaptoquinoline

et al. 2015

View full text Add to dashboard Cite

A series of ruthenium styryl complexes with potentially noninnocent κ 2 [N,O] − or κ 2 [N,S] − ligands have been prepared by treatment of 5-coordinated 16-valence-electron ruthenium styryl complexes Ru(CO)Cl(P i Pr 3 ) 2 (CHCH-C 6 H 4 -4R) with deprotonated bidentate 2-hydroxy-or 2-mercaptopyridines or 2-hydroxy-or 2-mercaptoquinolines. These 6-coordinated complexes have been characterized by NMR and IR spectroscopy and by cyclic voltammetry. Moreover, the structures of complexes 1d, 2a, 3c, 5b, and 6b have been established by X-ray crystallography. Our results indicate that the pyridine-derived complexes exist as two isomers that differ with respect to the orientation of the κ 2 [N,O] − or κ 2 [N,S] − donor ligands relative to the CO and alkenyl ligands in the equatorial plane. The equilibrium between the two isomers is thermodynamically controlled. Thus, the relative amount of the minor isomer increases at higher temperatures. With the 2-hydroxyquinoline-or 2-mercaptoquinoline-derived ligands only one isomer is observed. Electrochemical studies show that these complexes undergo one or two reversible consecutive one-electron oxidations, the potentials of which respond to the electronic properties of the 4-substituent at the styryl ligand and those of the ancillary chelate ligand. Strong ligand contributions to the first oxidation of the complexes were experimentally verified by IR and EPR spectroelectrochemistry. Quantum chemical calculations reproduce our experimental results, including the positions of the Ru(CO) vibrational bands of the neutral complexes and of their corresponding radical cations. Our combined results indicate that the oxidation of all complexes is dominated by the styryl ligand, irrespective of the electronic nature of the 4-substituent and of the [N,O] − or [N,S] − chelate ligand.

show abstract

“…The two double bonds are in a trans configuration. The overall geometry of complex 1 closely resembles those of the bimetallic ruthenium complexes [RuCl(CO)(PMe 3 ) 3 ] 2 (l-CH@CH-Ar-CH@CH) [35,42]. …”

Section: Description Of the Structurementioning

confidence: 77%

Synthesis, characterization, and properties of binuclear ruthenium complexes with dendritic side chains on their bridges

Liang

Xia

et al. 2011

Inorganica Chimica Acta

Self Cite

View full text Add to dashboard Cite

Synthesis, Characterization, and Substituent Effects of Binuclear Ruthenium Vinyl Complexes [RuCl(CO)(PMe₃)₃]₂(μ-CH═CH−Ar−CH═CH)

Cited by 55 publications

References 146 publications

Conformational Tuning of the Intramolecular Electronic Coupling in Molecular‐Wire Biruthenium Complexes Bridged by Biphenyl Derivatives

Conformational Tuning of the Intramolecular Electronic Coupling in Molecular‐Wire Biruthenium Complexes Bridged by Biphenyl Derivatives

Ruthenium Styryl Complexes with Ligands Derived from 2-Hydroxy- and 2-Mercaptopyridine and 2-Hydroxy- and 2-Mercaptoquinoline

Synthesis, characterization, and properties of binuclear ruthenium complexes with dendritic side chains on their bridges

Contact Info

Product

Resources

About