Synthesis, characterization, and substituent effects of mononuclear ruthenium complexes [RuCl(CO)(PMe3)3(CHCH-C6H4-R-p)] (R=H, CH3, OCH3, NO2, NH2, NMe2)

Wu, Xianghua; Weng, Tanqing; Jin, Shan; Liu, Jinghua; Guo, Rui; Yu, Guang‐Ao; Liu, Sheng Hua

doi:10.1016/j.jorganchem.2009.01.024

Cited by 22 publications

(27 citation statements)

References 79 publications

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“…The metal center in 3a exhibits a distorted octahedral geometry, consistent with previous examples [28,46]. The vinyl ligand is co-planar with the CO moiety (C(23)-…”

Section: Molecular Structuressupporting

confidence: 83%

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Syntheses, structures and redox properties of tris(pyrazolyl)borate-capped ruthenium vinyl complexes

Farmer

Man

Fox

et al. 2012

Journal of Organometallic Chemistry

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2012) 'Syntheses, structures and redox properties of tris(pyrazolyl)borate-capped ruthenium vinyl complexes.', Journal of organometallic chemistry., 721-722 . pp. 173-185. Further information on publisher's website:http://dx.doi.org/10.1016/j.jorganchem.2012.09.001Publisher's copyright statement: NOTICE: this is the author's version of a work that was accepted for publication in 'Journal of organometallic chemistry'. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reected in this document. Changes may have been made to this work since it was submitted for publication. A denitive version was subsequently published in Journal of organometallic chemistry, 721, 15 December 2012721, 15 December , 10.1016721, 15 December /j.jorganchem.2012 Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details.

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“…The metal center in 3a exhibits a distorted octahedral geometry, consistent with previous examples [28,46]. The vinyl ligand is co-planar with the CO moiety (C(23)-…”

Section: Molecular Structuressupporting

confidence: 83%

“…The five-coordinate species are convenient precursors to a range of derivatives through ligand substitution reactions [37][38][39][40][41][42][43][44], giving considerable scope to tune the metal-ligand coordination sphere. [18] and Ru(CH=CHR)(Cl)(CO)(PMe 3 ) 3 [28,46].…”

Section: Introductionmentioning

confidence: 99%

Syntheses, structures and redox properties of tris(pyrazolyl)borate-capped ruthenium vinyl complexes

Farmer

Man

Fox

et al. 2012

Journal of Organometallic Chemistry

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“…Others were commercially available. The starting materials [RuHCl (CO)(PPh 3 ) 3 ],73 2,7‐diiodofluorene ( 1 a ),74 2,7‐diiodo‐9,10‐dihydrophenanthrene ( 1 b ),60 4,4′‐diiodo‐2,2′‐dimethylbiphenyl ( 1 d ),60 4,4′‐diiodo‐2,2′,6,6′‐tetramethylbiphenyl ( 1 e ),75 and [RuCl(CO)(PMe 3 ) 3 (CHCHC 6 H 5 )] ( 5 )76 were prepared by the procedures described in the literature.…”

Section: Methodsmentioning

confidence: 99%

“…Others were commercially available. The starting materials [RuHCl (CO)(PPh 3 ) 3 ], [73] 2,7-diiodofluorene (1a), [74] 2,7-diiodo-9,10-dihydrophenanthrene (1b), [60] 4,4'-diiodo-2,2'-dimethylbiphenyl (1d), [60] 4,4'-diiodo-2,2',6,6'-tetramethylbiphenyl (1e), [75] and [RuCl(CO)(PMe 3 ) 3 (CH=CHC 6 H 5 )] (5) [76] were prepared by the procedures described in the literature. Synthesis of diethynyl biphenyl derivatives 2,7-Bis(ethynyl)fluorene (3 a):2 ,7-Bis(trimethylsilylethynyl)fluorene (2a,0 .36 g, 1mmol) was dissolved in am ixture of THF (6 mL) and methanol (6 mL).…”

Section: Experimental Section General Materialsmentioning

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

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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.

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“…This conformational preference is driven by stabilizing secondary interactions between the filled π orbitals of the alkenyl ligand and the CO π* acceptor orbitals and observed for most complexes of this kind. 45 The torsion of the vinylic double bond of −20.6 (5) indicative of significant π conjugation between the Ru(CO)Cl-(P i Pr 3 ) 2 moiety and the styryl ligand. The observed rotation out of the conjugation plane may in part be due to strong intermolecular hydrogen-bonding interactions that involve both hydrogen atoms of the 4-amino substituent of the styryl ligand.…”

Section: ■ Introductionmentioning

confidence: 99%

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

et al. 2015

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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.

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Synthesis, characterization, and substituent effects of mononuclear ruthenium complexes [RuCl(CO)(PMe3)3(CHCH-C6H4-R-p)] (R=H, CH3, OCH3, NO2, NH2, NMe2)

Cited by 22 publications

References 79 publications

Syntheses, structures and redox properties of tris(pyrazolyl)borate-capped ruthenium vinyl complexes

Syntheses, structures and redox properties of tris(pyrazolyl)borate-capped ruthenium vinyl complexes

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

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