Dinuclear Ruthenium(III)–Ruthenium(IV) Complexes, Having a Doubly Oxido-Bridged and Acetato- or Nitrato-Capped Framework

Suzuki, Takehito; Suzuki, Yutaka; Kawamoto, Tatsuya; Miyamoto, Ryo; Nanbu, Shinkoh; Nagao, Hidemi

doi:10.1021/acs.inorgchem.6b00890

Cited by 15 publications

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“…Only one reduction is seen for compounds 1 – 7 within the cathodic limit of water (i.e., ∼−1.0 V vs SCE) while two reductions are seen for the same compounds within the cathodic limit of DMSO (i.e., ∼−2.2 V vs SCE). On the basis of the well-characterized electrochemical behavior for these types of diruthenium complexes in nonaqueous solvents, − ,,,− the first electron transfer is assigned to the Ru 2 5+ /Ru 2 4+ redox couple in H 2 O or DMSO, while the second process in DMSO is attributed to a Ru 2 4+ /Ru 2 3+ electrode reaction. As shown in Figure b and Table , only the Ru 2 5+ /Ru 2 4+ process is reversible in DMSO.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Structural and Physicochemical Properties of Water-Soluble Mixed-Ligand Diruthenium Complexes Containing Anilinopyridinate Bridging Ligands

et al. 2019

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A series of water-soluble Ru 2 5+ complexes of the type Ru 2 (O 2 CCH 3 ) 3 (L)Cl where L = 2,3,4,5,6-F 5 ap, 2,4,6-F 3 ap, 2-Fap, ap, 2-Meap, 2,6-Me 2 ap, or 2,4,6-Me 3 ap, where ap is the anilinopyridinate anion, have been characterized as to their structural and physicochemical properties in H 2 O and DMSO. Five of the newly synthesized complexes were structurally characterized, and the Ru−Cl bond lengths range from 2.477 to 2.544 Å while the Ru−Ru bond lengths range from 2.2838 to 2.2935 Å. The UV−vis spectra of each compound are characterized by three absorption bands in both H 2 O and DMSO, the intensity and position of which vary with both the type of bridging ligand and the solvent. The seven examined Ru 2 5+ complexes exist as 1:1 electrolytes in water, and each undergoes a reversible one-electron reduction assigned to Ru 2 5+ /Ru 2 4+ in both investigated solvents. A second irreversible reduction attributed to Ru 2 4+ /Ru 2 3+ is also observed for each compound at more negative potentials in DMSO. A linear free energy relationship exists between the sum of the Hammett substituent constants (Σσ) on the ap-type bridging ligand and the wavenumber of an absorption band for the Ru 2 5+ complexes. A linear relationship is also seen between Σσ and measured E 1/2 values for the Ru 2 5+ /Ru 2 4+ process in water containing 0.1 M KCl, but little to no effect is seen between the specific bridging ligand and the structural features of the investigated compounds.

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Section: Resultsmentioning

confidence: 99%

Synthesis, Structural and Physicochemical Properties of Water-Soluble Mixed-Ligand Diruthenium Complexes Containing Anilinopyridinate Bridging Ligands

et al. 2019

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“…A reaction of [ 2 Cl ] + with silver salts was investigated to pull out chlorido ligands. In water–acetone, a reaction of [ 2 Cl ] + and [ 2′ Cl ] + with two equimolar amounts of AgNO 3 afforded corresponding singly oxido-bridged complexes containing terminal aqua and hydroxido ligands, [{Ru III Cl(OH 2 )(Rbpma)}(μ-O){Ru IV Cl(OH)(Rbpma)}] 2+ ([ 2 H 2 O‑OH )] 2+ and [ 2′ H 2 O‑OH ] 2+ ), whereas those of [ 2 Cl ] + with four equimolar amounts of AgCH 3 COO induced structural changes to form a doubly oxido-bridged complex having an acetate as an oxygen donor bidentate ligand, [{Ru III,IV (ebpma)} 2 (μ-O) 2 (μ-O 2 CCH 3 )] 2+ ([ 3 CH 3 COO ] 2+ ) . The protonation at one of the bridging oxido ligands of [ 3 CH 3 COO ] 2+ occurred in a pH 1 aqueous solution to afford a complex having the {Ru 2 (μ-O)(μ-OH)} core, [{Ru III,IV (ebpma)} 2 (μ-O)(μ-OH)(μ-O 2 CCH 3 )] 3+ ([ 3H + CH 3 COO ] 3+ ).…”

Section: Resultsmentioning

confidence: 99%

“…In UV–vis–near-infrared (NIR) absorption spectra, the singly bridged complexes of Ru III –Ru IV , [ 2′ Cl ] + , [ 2 Cl ] + , and [ 2 H 2 O‑OH ] 2+ , showed a weak broad band in the NIR region in acetonitrile (Figure and Table ), which was assigned to an intervalence charge transfer (IVCT) band as one of the characteristics to the mixed-valence state. On the other hand, the triply bridged complexes of Ru III –Ru IV , [ 3 L ] 2+ , exhibited a broad absorption band which was more intense than that of the singly bridged complexes, shown around 700–900 nm in acetonitrile (Figure and Table ) and was assigned to the electronic transitions on the {Ru 2 (μ-O) 2 } core. [ 2 X ] m + showed the IVCT band because of an unpaired electron transferred through the dπ(Ru)–pπ(O)–dπ(Ru) orbitals on the {Ru 2 (μ-O)} core, whereas for [ 3 L ] 2+ , it was through the dπ(Ru)–dπ(Ru) orbitals on the {Ru 2 (μ-O) 2 } core.…”

Section: Resultsmentioning

confidence: 99%

“…[{Ru II,II (bbpma)} 2 (μ-Cl) 3 ]PF 6 ([ 1′ ]PF 6 ) was synthesized in a manner similar to that of [{Ru II,II (ebpma)} 2 (μ-Cl) 3 ]PF 6 ([ 1 ]PF 6 ) . [{Ru III,IV Cl 2 (ebpma)} 2 (μ-O)]PF 6 was prepared by the procedure reported in ref and [{Ru III,IV (ebpma)} 2 (μ-O) 2 (μ-O 2 CCH 3 )](PF 6 ) 2 ([ 3 CH 3 COO ](PF 6 ) 2 ) in ref . The corresponding ClO 4 salt complexes, [ 2 Cl ]ClO 4 and [ 3 CH 3 COO ](ClO 4 ) 2 , were prepared in manners similar to those of the PF 6 salt by using NaClO 4 instead of NH 4 PF 6 .…”

Section: Methodsmentioning

confidence: 99%

“…The structures of [ 2′ Cl ] + , [ 3 CH 3 COO ] 2+ , and [ 3H + CH 3 COO ] 3+ are shown in Figures , , and S1, respectively. Crystallographic data and selected bond lengths and angles are summarized in Tables S1, S2, and along with those of previously reported singly and triply bridged complexes, [ 2 Cl ] + and [ 3 NO 3 ] 2+ . The intensity data of X-ray crystallography were collected on a Rigaku Mercury CCD diffractometer using graphic monochromatized Mo Kα radiation (λ = 0.710747 Å) or on a Rigaku XtaLAB P200 or Synergy-S diffractometer using multilayer mirror monochromated Cu Kα radiation (λ = 1.54184 Å).…”

Section: Methodsmentioning

confidence: 99%

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Framework Conversion of Oxido-Bridged Dinuclear Ruthenium Complexes

et al. 2019

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Syntheses, properties, and reactions of hydroxido-or oxido-bridged dinuclear ruthenium complexes bearing a tridentate auxiliary ligand, ethylbis(2-pyridylmethyl)amine (ebpma) or benzylbis(2-pyridylmethyl)amine (bbpma), have been investigated. Reduction reactions of a singly oxidob r i d g e d d i r u t h e n i u m c o m p l e x b e a r i n g e b p m a , [{Ru III,IV Cl 2 (ebpma)} 2 (μ-O)] + ([2 Cl ] + ), by zinc in acetonitrile afforded an acetonitrile-substituted singly oxido-bridged complex in the Ru III −Ru III isovalent state, [{Ru III,III Cl(NCCH 3 )(ebpma)} 2 (μ-O)] 2+ ([2 CH 3 CN ] 2+ ). Chlorido ligand abstraction reactions using silver salts have also been attempted. Through a reaction of [2 Cl ] + with two equimolar amounts of AgNO 3 in water−acetone, a singly oxido-bridged complex having an aqua and a hydroxido, [{Ru III Cl(OH 2 )(ebpma)}(μ-O){Ru IV Cl-(OH)(ebpma)}] 2+ ([2 H 2 O-OH ] 2+ ), was obtained. Reactions with four equimolar amounts of AgL (L = CH 3 COO − or NO 3 − ) in water−acetone gave doubly oxido-and bidentate oxygen donor ligand-bridged diruthenium complexes of Ru(III)−Ru(IV), [{Ru III,IV (ebpma)} 2 (μ-O) 2 (μ-L)] 2+ ([3 L ] 2+ ; L = O 2 CCH 3 ; [3 CH 3 COO ] 2+ , L = O 2 NO; [3 NO 3 ] 2+ ). Reactions of [3 L ] 2+ under acidic conditions afforded a corresponding one-protonated species having the {Ru 2 (μ-O)(μ-OH)} core. Reactivity and electronic structure of the oxido-bridged diruthenium complexes were studied by electrochemical, spectroscopic, and theoretical methods.

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