Ru(CH3CN)3Cl3, preparation and use as a mediator for the electrooxidation of hydrocarbons

Appelbaum, L.; Heinrichs, C.; Demtschuk, Jörg; Michman, M.; Oron, Miriam; Schäfer, Hans J.; Schumann, Herbert

doi:10.1016/s0022-328x(99)00532-x

Cited by 20 publications

(26 citation statements)

References 31 publications

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“…À resembles those in previous reports (Gheller et al, 1995;Appelbaum et al, 1999;Jabłoń skaWawrzycka et al, 2013). The Ru III ion adopts an octahedral coordination geometry, with four Cl atoms occupying equatorial positions and two acetonitrile molecules in the axial positions.…”

Section: Structure Descriptionsupporting

confidence: 90%

2-[Tris(pyridin-2-yl)methyl]pyridiniumtrans-bis(acetonitrile)tetrachloridoruthenate(III) acetonitrile monosolvate

2017

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The asymmetric unit of the title compound, [(C 5 H 4 N) 3 C(C 5 H 5 N)][RuCl 4 -(CH 3 CN) 2 ]ÁCH 3 CN, contains one 2-[tris(pyridin-2-yl)methyl]pyridinium cation, one trans-bis(acetonitrile)tetrachloridoruthenate(III) anion and one acetonitrile solvent molecule. The Ru III ion is coordinated by four Cl À anions in the equatorial plane and by two acetonitrile ligands in the axial positions, forming a distorted octahedral geometry. The cation, the monoprotonated species of tetrakis(pyridin-2-yl)methane, forms an intramolecular N-HÁ Á ÁN hydrogen bond between the pyridinium ring and one of the pyridine rings. The complex anions are linked to each other via C-HÁ Á ÁCl hydrogen bonds, forming an undulating sheet parallel to the ac plane. A C-HÁ Á ÁN hydrogen bond between the cation and the anion is also observed. The solvate acetonitrile molecule forms C-HÁ Á ÁN and C-HÁ Á ÁCl hydrogen bonds, respectively, with the cation and the anion. Structure descriptionWe have investigated the synthesis and properties of tetrakis(pyridin-2-yl)methane (py 4 C) over the last decade (Matsumoto et al., 2003(Matsumoto et al., , 2004. In the course of our studies on py 4 C, we are interested in the ruthenium complex with py 4 C because of the fascinating properties of ruthenium polypyridine complexes (Juris et al., 1988;Balzani et al., 1996). Although we did not obtain the desired ruthenium complex, we obtained single crystals of the title compound instead. This is the first report of the crystal structure including the monoprotonated py 4 C cation, [(py 4 C)ÁH] + .

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Section: Structure Descriptionsupporting

confidence: 90%

2-[Tris(pyridin-2-yl)methyl]pyridiniumtrans-bis(acetonitrile)tetrachloridoruthenate(III) acetonitrile monosolvate

2017

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“…[25] No structural data seem to be available for Ru III complexes with the stoichiometry [RuX 3 (PR 3 ) 3 ] with X = any halogen. However, crystallographically characterized [RuCl 3 (L) 3 ] complexes exist, for instance with L = MeCN [26] or L 3 = terpy. [27] The optimized geometrical parameters compared quite well with the experimental data in all cases.…”

Section: Resultsmentioning

confidence: 99%

An Experimental and Computational Study on the Effect of Al(OiPr)₃ on Atom‐Transfer Radical Polymerization and on the Catalyst—Dormant‐Chain Halogen Exchange

Poli

Stoffelbach

Maria

et al. 2005

Chemistry A European J

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Compound Al(OiPr)3 is shown to catalyze the halide-exchange process leading from [Mo(Cp)Cl2(iPrN=CH-CH=NiPr)] and CH3CH(X)COOEt (X=Br, I) to the mixed-halide complexes [Mo(Cp)ClX(iPrN=CH-CH=NiPr)]. On the other hand, no significant acceleration is observed for the related exchange between [MoX3(PMe3)3] (X=Cl, I) and PhCH(Br)CH3, by analogy to a previous report dealing with the Ru(II) complex [RuCl2(PPh3)3]. A DFT computation study, carried out on the model complexes [Mo(Cp)Cl2(PH3)2], [MoCl3(PH3)3], and [RuCl2(PH3)3], and on the model initiators CH3CH(Cl)COOCH3, CH3Cl, and CH3Br, reveals that the 16-electron Ru(II) complex is able to coordinate the organic halide RX in a slightly exothermic process to yield saturated, diamagnetic [RuCl2(PH3)3(RX)] adducts. The 15-electron [MoCl3(PH3)3] complex is equally capable of forming an adduct, that is, the 17-electron [MoCl3(PH3)3(CH3Cl)] complex with a spin doublet configuration, although the process is endothermic, because it requires an energetically costly electron-pairing process. The interaction between the 17-electron [Mo(Cp)Cl2(PH3)2] complex and CH3Cl, on the other hand, is repulsive and does not lead to a stable 19-electron adduct. The [RuCl2(PH3)3(CH3X)] system leads to an isomeric complex [RuClX(PH3)3(CH3Cl)] by internal nucleophilic substitution at the carbon atom. The transition state of this process for X=Cl (degenerate exchange) is located at lower energy than the transition state required for halogen-atom transfer leading to [RuCl3(PH3)3] and the free radical CH3. On the basis of these results, the uncatalyzed halide exchange is interpreted as the result of a competitive S(N)i process, whose feasibility depends on the electronic configuration of the transition-metal complex. The catalytic action of Al(OiPr)3 on atom-transfer radical polymerization (and on halide exchange for the 17-electron half-sandwich Mo(III) complex) results from a more favorable Lewis acid-base interaction with the oxidized metal complex, in which the transferred halogen atom is bound to a more electropositive element. This conclusion derives from DFT studies of the model [Al(OCH3)3]n (n=1,2,3,4) compounds, and on the interaction of Al(OCH3)3 with CH3Cl and with the [Mo(Cp)Cl3(PH3)2] and [RuCl3(PH3)3] complexes.

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“…Ruthenium and its compounds have been widely used especially in the field of homogeneous and heterogeneous catalysis, including electrocatalysis and photocatalysis 1–8 . Their catalytic activity as it relates to oxidation and reduction as well as other reactions (e.g., dimerization, polymerization) strongly depends on their oxidation state (ruthenium displays ten oxidation states) and on the media used, because of the formation of different simple and polynuclear complexes.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Nanogravimetric Studies of Ruthenium(III) Trichloride Microcrystals

Inzelt

Róka

2008

Israel Journal of Chemistry

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Ruthenium (III) trichlorid solid crystals have been mechanically attached to gold and paraffin‐impregnated graphite surfaces and studied in the presence of aqueous solutions of M+Cl− electrolytes, where M+ = Li+, Na+, K+, Rb+, Cs+ and K2SO4 by cyclic voltammetry and electrochemical nanogravimetry at a quartz crystal microbalance (EQCM). The electrochemical reduction of the layered α‐RuCl3 microcrystals causes drastic changes in the composition and the structure of crystals. The comparison of the current—potential and surface mass change—potential functions belonging to the first reduction‐reoxidation cycle with the subsequent ones reveals that the simple intercalation scheme described in the literature cannot be entirely valid. During the first reduction step at ca. 0.2 V vs. SCE the charge consumption is substantially higher than in the course of the further potential cycling, and the simultaneous rapid and intense mass decrease indicates that considerable chemical and structural transformations occurs. Although a loss of the surface mass cannot be entirely excluded, the frequency increase most likely is not related to the dissolution of the microcrystals, however, large amounts of water molecules and—to a much smaller extent—chloride ions leave the crystal phase, and in fact a new material, which remains strongly attached to the gold or graphite surface, is formed. The extremely high frequency change at the first reduction process during the first cycle is most likely related to the stress effect originating in the phase transition of the surface layer and/or the removal of the water rigidly coupled to the surface into voids of the immobilized microcrystals. Depending on the amount of microcrystals on the electrode surface and the experimental conditions (the nature and concentration of the contacting electrolyte, scan rate, and potential range) used, after the “break‐in” cycle stable electrochemical and nanogravimetric responses develop. The several reduction and reoxidation pairs of waves in the cyclic voltammograms and the simultaneous mass changes are in connection with the wide variety of intercalation reactions and complex formation during the electrochemical transformations. The mass change was reversible, in general, during reduction mass increase, while during oxidation mass decrease occurred at medium electrolyte concentrations in three or more steps. The mass excursions are rather complicated, involving different mass increase/decrease regions as a function of potential and the composition of the contacting solution. Taking into account the layered structure of RuCl3, the electrochemical reduction can be explained as an intercalation reaction in that mixed valence intercalation phases with a general formula K n+ Ru z‐nIII [Ru nII Cl3z‐y (H2O)y] • dH2O are formed from z (RuCl3 · H2O). The reduction/reoxidation waves are related to the redox transformations of Ru(III) to Ru(II) sites and the insertion/deinsertion of cations and water molecules, while the composition of the polynuclear complexe...

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Ru(CH3CN)3Cl3, preparation and use as a mediator for the electrooxidation of hydrocarbons

Cited by 20 publications

References 31 publications

2-[Tris(pyridin-2-yl)methyl]pyridiniumtrans-bis(acetonitrile)tetrachloridoruthenate(III) acetonitrile monosolvate

2-[Tris(pyridin-2-yl)methyl]pyridiniumtrans-bis(acetonitrile)tetrachloridoruthenate(III) acetonitrile monosolvate

An Experimental and Computational Study on the Effect of Al(OiPr)₃ on Atom‐Transfer Radical Polymerization and on the Catalyst—Dormant‐Chain Halogen Exchange

Electrochemical Nanogravimetric Studies of Ruthenium(III) Trichloride Microcrystals

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Ru(CH3CN)3Cl3, preparation and use as a mediator for the electrooxidation of hydrocarbons

Cited by 20 publications

References 31 publications

2-[Tris(pyridin-2-yl)methyl]pyridiniumtrans-bis(acetonitrile)tetrachloridoruthenate(III) acetonitrile monosolvate

2-[Tris(pyridin-2-yl)methyl]pyridiniumtrans-bis(acetonitrile)tetrachloridoruthenate(III) acetonitrile monosolvate

An Experimental and Computational Study on the Effect of Al(OiPr)3 on Atom‐Transfer Radical Polymerization and on the Catalyst—Dormant‐Chain Halogen Exchange

Electrochemical Nanogravimetric Studies of Ruthenium(III) Trichloride Microcrystals

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An Experimental and Computational Study on the Effect of Al(OiPr)₃ on Atom‐Transfer Radical Polymerization and on the Catalyst—Dormant‐Chain Halogen Exchange