Synthesis and Structural and Physicochemical Characterization of {[Rh2(μ‐OOCCH3)2(dmbpy)2][BF4]}n Molecular Wire

Rak, Magdalena; Pruchnik, Florian P.; Ciunik, Zbigniew; Lafolet, Frédéric; Chardon‐Noblat, Sylvie; Deronzier, Alain

doi:10.1002/ejic.200800822

Cited by 8 publications

(3 citation statements)

References 28 publications

(61 reference statements)

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“…The band at 566 nm for the MeCN solution of [ 1 ](PF 6 ) 2 that can be assigned as a π*(Rh–Rh) to σ*(Rh–Rh) transition shifted to 605 nm for the MeOH solution. Similar shifts between N-donor solvents and O-donor solvents have been reported for paddlewheel or other M–M-bonded dirhodium complexes. ,, This means that [ 1 ] 2+ exists as [ 1 (MeCN) 2 ] 2+ and [ 1 (MeOH) 2 ] 2+ in MeCN and MeOH, respectively. The 1 H NMR spectra of [ 1 Cl 2 ] and [ 1 ](PF 6 ) 2 in CD 3 OD are quite similar to each other (Figure S1, Supporting Information), but the absorption spectrum for [ 1 Cl 2 ] in MeOH is slightly different from that for [ 1 ](PF 6 ) 2 in MeOH.…”

Section: Resultssupporting

confidence: 77%

Mixed Valency in Quadruple Hydrogen-Bonded Dimers of Bis(biimidazolate)dirhodium Complexes

et al. 2015

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Dirhodium complexes with biimidazole (H2bim) ligands [Rh2(O2CR)2(H2bim)2Cl2] (R = Bu ([1Cl2]), Pr ([2Cl2])), [Rh2(O2CBu)2(H2bim)2](PF6)2 ([1](PF6)2), [Rh2(O2CBu)2(H2bim)2(PPh3)2](PF6)2 ([1(PPh3)2](PF6)2), and [Rh2(O2CPr)2(H2bim)2(PPh3)2]Cl2 ([2(PPh3)2]Cl2) have been synthesized. Deprotonation of the biimidazole complexes afforded the quadruply hydrogen-bonded dimers of the biimidazolate complexes [Rh2(O2CR)2(Hbim)2(PPh3)2]2 (R = Bu ([1'(PPh3)2]2) and Pr ([2'(PPh3)2]2)). Complementary hydrogen bonds between the Hbim(-) ligands are not coplanar because the Hbim(-) ions in one dirhodium complex are not parallel (the dihedral angle between them is ca. 15°). A cyclic voltammogram of [1'(PPh3)2]2 shows two sets of two consecutive oxidation waves in CH2Cl2. The one-electron-oxidized species of [1'(PPh3)2]2 showed no intervalence charge-transfer band in the electronic spectrum and an axially symmetrical ESR spectrum with hyperfine structure because of two phosphorus atoms. These observations show that the odd electron is localized in a σ(Rh-Rh) orbital on one dirhodium unit. Theoretical calculations indicate that an oxidized complex [Rh2(O2CMe)2(bim)2(PMe3)2](-) hydrogen bonded with a biimidazole complex [Rh2(O2CMe)2(H2bim)2(PMe3)2](2+) was a stable mixed-valence complex.

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Section: Resultssupporting

confidence: 77%

Mixed Valency in Quadruple Hydrogen-Bonded Dimers of Bis(biimidazolate)dirhodium Complexes

et al. 2015

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“…Polymetallic compounds belonging to this class are believed to find application as conducting molecular wires in the expanding field of molecular electronics and nanoscale molecular devices . More recently, several related complexes, {[Rh 2 (NN) 2 (μ-O 2 CMe) 2 ](BX 4 )} n (NN = 2,2′-bipyridine (bpy) or 1,10-phenanthroline; X = F, Ph), have been prepared and characterized by Pruchnik et al, , some of them exhibiting interesting redox behavior. , …”

Section: Introductionmentioning

confidence: 99%

Soluble Redox-Active Polymetallic Chains [{Ru⁰(CO)(L)(bpy)}^m]_n (bpy = 2,2′-bipyridine, L = PrCN, Cl⁻; m = 0, −1): Electrosynthesis and Characterization

et al. 2009

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Electrochemical and spectroelectrochemical techniques were employed to study in detail the formation and so far unreported spectroscopic properties of soluble electroactive molecular chains with nonbridged metal-metal backbones, namely, [{Ru(0)(CO)(PrCN)(bpy)}(m)](n) (m = 0, -1) and [{Ru(0)(CO)(bpy)Cl}(m)](n) (m = -1, -2; bpy = 2,2'-bipyridine). The precursors cis-(Cl)-[Ru(II)(CO)(MeCN)(bpy)Cl(2)] (in PrCN) and mer-[Ru(II)(CO)(bpy)Cl(3)](-) (in tetrahydrofuran (THF) and PrCN) undergo one-electron reductions to reactive radicals [Ru(II)(CO)(MeCN)(bpy(*-))Cl(2)](-) and [Ru(II)(CO)(bpy(*-))Cl(3)](2-), respectively. Both [bpy(*-)]-containing species readily electropolymerize on concomitant dissociation of two chloride ligands and consumption of a second electron. Along this path, mer-to-fac isomerization of the bpy-reduced trichlorido complex (supported by density functional theory calculations) and a concentration-dependent oligomerization process contribute to the complex reactivity pattern. In situ spectroelectrochemistry (IR, UV/vis) has revealed that the charged polymer [{Ru(0)(CO)(bpy)Cl}(-)](n) is stable in THF, but in PrCN it converts readily to [Ru(0)(CO)(PrCN)(bpy)](n). An excess of chloride ions retards this substitution at low temperatures. Both polymetallic chains are completely soluble in the electrolyte solution and can be reduced reversibly to the corresponding [bpy(*-)]-containing species.

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“…These compounds exhibit unusual semiconductivity and magnetic properties as well as a rich redox activity. 9,10 Another class of metal-metal bonded chain complexes are those based on ruthenium and osmium. The first example of such polymetallic compounds is the simple [Ru(CO) 4 ] n polymer which has been reported for the first time in 1986 11 and structurally characterized later by X-ray diffraction.…”

Section: Introductionmentioning

confidence: 99%

Structural characterization of metal–metal bonded polymer [Ru(L)(CO)2]n (L = 2,2′-bipyridine) in the solid state using high-resolution NMR and DFT chemical shift calculations

Gerbaud

Mouesca

Hediger

et al. 2010

Phys. Chem. Chem. Phys.

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The metal bonded ruthenium polymer [Ru(0)(bpy)(CO)(2)](n) (bpy = 2,2'-bipyridine) is known to be a very promising and efficient solid material for catalysis applications, such as carbon dioxide electroreduction in pure aqueous media and the water-gas shift reaction. It also exhibits potential application for molecular electronics as a conductive molecular wire. The insolubility and relative air-sensitivity of [Ru(0)(bpy)(CO)(2)](n) as well as the lack of monocrystals make its structural characterization very challenging. A first approach to determine the structure of this polymer has been obtained by ab initio X-ray powder diffraction, based on the known X-ray structure of [Ru(CO)(4)](n). In order to refine this structure, a non-conventional solid-state NMR study was performed. The results of this study are presented here. The comparison of high-resolution solid-state (13)C NMR spectra of the polymer with those of the corresponding monomeric [Ru(bpy)(CO)(2)Cl(2)] or dimeric [Ru(bpy)(CO)(2)Cl](2) precursor complexes has shown a clear shift and splitting of carbonyl ligand resonances, which turns out to be linearly correlated with the redox state of the Ru (ii, i or 0, respectively). Bipyridine resonances are also affected but in a non-trivial way. Finally, in the case of the dimer, it was found that the CO peak splitting (2.7 ppm) contains structural information, e.g. the ligand staggering angle. Based on DFT chemical shift calculations on corresponding model molecules (n = 1-2), all the described experimental observations could be reproduced. Moreover, upon extending these calculations to models of increasing length (n = 3-5), it turns out that information about the staggering angle between successive ligands is actually retained in the CO NMR computed peak splitting. Turning back to experiments, the CO broad signal measured for the wire could be decomposed into a major component (at 214.9 ppm) assigned to the internal CO ligands, and a minor doublet component (216.9 and 218.1 ppm) whose splitting (2.8 ppm) contains the staggering angle information. Finally, from the relative integrals of these three components, expected to be in the ratio 1 : 1 : n-2, it was possible to tentatively estimate the length n of the polymetallic wire (n = 7).

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Synthesis and Structural and Physicochemical Characterization of {[Rh₂(μ‐OOCCH₃)₂(dmbpy)₂][BF₄]}_n Molecular Wire

Cited by 8 publications

References 28 publications

Mixed Valency in Quadruple Hydrogen-Bonded Dimers of Bis(biimidazolate)dirhodium Complexes

Mixed Valency in Quadruple Hydrogen-Bonded Dimers of Bis(biimidazolate)dirhodium Complexes

Soluble Redox-Active Polymetallic Chains [{Ru⁰(CO)(L)(bpy)}^m]_n (bpy = 2,2′-bipyridine, L = PrCN, Cl⁻; m = 0, −1): Electrosynthesis and Characterization

Structural characterization of metal–metal bonded polymer [Ru(L)(CO)2]n (L = 2,2′-bipyridine) in the solid state using high-resolution NMR and DFT chemical shift calculations

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Synthesis and Structural and Physicochemical Characterization of {[Rh2(μ‐OOCCH3)2(dmbpy)2][BF4]}n Molecular Wire

Cited by 8 publications

References 28 publications

Mixed Valency in Quadruple Hydrogen-Bonded Dimers of Bis(biimidazolate)dirhodium Complexes

Mixed Valency in Quadruple Hydrogen-Bonded Dimers of Bis(biimidazolate)dirhodium Complexes

Soluble Redox-Active Polymetallic Chains [{Ru0(CO)(L)(bpy)}m]n (bpy = 2,2′-bipyridine, L = PrCN, Cl−; m = 0, −1): Electrosynthesis and Characterization

Structural characterization of metal–metal bonded polymer [Ru(L)(CO)2]n (L = 2,2′-bipyridine) in the solid state using high-resolution NMR and DFT chemical shift calculations

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Synthesis and Structural and Physicochemical Characterization of {[Rh₂(μ‐OOCCH₃)₂(dmbpy)₂][BF₄]}_n Molecular Wire

Soluble Redox-Active Polymetallic Chains [{Ru⁰(CO)(L)(bpy)}^m]_n (bpy = 2,2′-bipyridine, L = PrCN, Cl⁻; m = 0, −1): Electrosynthesis and Characterization