Brief introduction of Dichloro(benzene)ruthenium(II) dimer

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A catalyst contains a metal complex compound represented by the following general formula (I). In the formula (I), M is a metal ion such as ruthenium, L1 is a cyclic or acyclic, neutral or minus 1-valent unsaturated hydrocarbon group of 1 to 30 carbon atoms which may have a substituent, L2 and L3 are each independently chlorine or the like, and L4 is a compound bonded to M through phosphorus or arsenic and represented by the following general formula (IIa) or (IIb). In the formulas (IIa) and (IIb), E is phosphorus or arsenic, Y1 is oxygen or sulfur, Y2, Y3 and Y4 are each independently a hydrogen atom, an aryl group or the like, and H is a hydrogen atom.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

Archives for Chemistry Experiments of Dichloro(benzene)ruthenium(II) dimer

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Transfer news: A synthetic approach to chiral beta-CF3- substituted saturated carbonyl compounds has been developed in which ruthenium complexes efficiently catalyze the redox isomerization of CF3-bearing allylic alcohols by an intramolecular suprafacial enantiospecific 1,3-hydrogen transfer (see scheme). This method was used for the enantioselective synthesis of (S)-CF3-citronellol. Copyright

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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A series of Ru(ii) complexes were synthesised based on a hemilabile pyrazole-N-heterocyclic carbene (NHC)-pyrazole (C3N2H3)CH2(C3N2H2)CH2(C3N2H3) NCN pincer ligand 1. All complexes were fully characterised using single crystal X-ray crystallography and multinuclear NMR spectroscopy. Hemilabile ligands provide flexible coordination modes for the coordinating metal ion which can play a significant effect on the efficiency and mechanism of catalysis by the resulting complex. Here we observed and isolated mono-, bi- and tri-dentate complexes of both Ag(i) and Ru(ii) with 1 in which the resultant coordination mode was controlled by careful reagent selection. The catalytic activity of the Ru(ii) complexes for the transfer hydrogenation reaction of acetophenone with isopropanol was investigated. The unexpected formation of the pentaborate anion, [B5O6(OH)4]-, during the synthesis of complex 6a was found to have an unexpected positive effect by enhancing the catalysis rate. This work provides insights into the roles that different coordination modes, counterions and ligand hemilability play on the catalytic activity in transfer hydrogenations.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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[RuCl(arene)(mu-Cl)]2 dimers were treated in a 1:2 molar ratio with sodium or thallium salts of bis- and tris(pyrazolyl)borate ligands [Na(Bp Br 3)], [Tl(Tp Br 3)], and [Tl(TpiPr, 4Br)]. Mononuclear neutral complexes [RuCl(arene)(kappa2-Bp Br 3)] (1: arene=p-cymene (cym); 2: arene=hexamethylbenzene (hmb); 3: arene=benzene (bz)), [RuCl(arene) (kappa2-Tp Br 3)] (4: arene=cym; 6: arene=bz), and [RuCl(arene)(kappa2-TpiPr, 4Br)] (7: arene=cym, 8: arene=hmb, 9: arene=bz) have been always obtained with the exception of the ionic [Ru2(hmb)2(mu-Cl)3][Tp Br 3] (5?), which formed independently of the ratio of reactants and reaction conditions employed. The ionic [Ru(CH3OH)(cym)(kappa2-Bp Br 3)][X] (10: X=PF6, 12: X=O3SCF3) and the neutral [Ru(O2CCF3)(cym)(kappa2-Bp Br 3)] (11) have been obtained by a metathesis reaction with corresponding silver salts. All complexes 1-12 have been characterized by analytical and spectroscopic data (IR, ESI-MS, 1H and 13C NMR spectroscopy). The structures of the thallium and calcium derivatives of ligand Tp Br 3, [Tl(Tp Br 3)] and [Ca(dmso)6][Tp Br 3]2×2 DMSO, of the complexes 1, 4, 5?, 6, 11, and of the decomposition product [RuCl(cym)(HpziPr, 4Br)2][Cl] (7?) have been confirmed by using single-crystal X-ray diffraction. Electrochemical studies showed that 1-9 and 11 undergo a single-electron RuII?Ru III oxidation at a potential, measured by cyclic voltammetry, which allows comparison of the electron-donor characters of the bis- and tris(pyrazol-1-yl)borate and arene ligands, and to estimate, for the first time, the values of the Lever EL ligand parameter for Bp Br 3, Tp Br 3, and TpiPr, 4Br. Theoretical calculations at the DFT level indicated that both oxidation and reduction of the Ru complexes under study are mostly metal-centered with some involvement of the chloride ligand in the former case, and also demonstrated that the experimental isolation of the mu3-binuclear complex 5? (instead of the mononuclear 5) is accounted for by the low thermodynamic stability of the latter species due to steric reasons.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Over the past 20 years, ruthenium(II)-based dyes have played a pivotal role in turning dye-sensitized solar cells (DSCs) into a mature technology for the third generation of photovoltaics. However, the classic I3-/I- redox couple limits the performance and application of this technique. Simply replacing the iodine-based redox couple by new types like cobalt(3+/2+) complexes was not successful because of the poor compatibility between the ruthenium(II) sensitizer and the cobalt redox species. To address this problem and achieve higher power conversion efficiencies (PCEs), we introduce here six new cyclometalated ruthenium(II)-based dyes developed through ligand engineering. We tested DSCs employing these ruthenium(II) complexes and achieved PCEs of up to 9.4% using cobalt(3+/2+)-based electrolytes, which is the record efficiency to date featuring a ruthenium-based dye. In view of the complicated liquid DSC system, the disagreement found between different characterizations enlightens us about the importance of the sensitizer loading on TiO2, which is a subtle but equally important factor in the electronic properties of the sensitizers.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Highly conjugated perinones were evaluated as proligands with [Ru(eta6-arene)Cl2]2 precursors (arene = p-cymene or benzene). None of them, except itaco-perinone (IP) bearing one exocyclic methylene group, were able to form coordination compounds. Expected eta1-coordination through the lone pair of the nitrogen or oxygen atoms of the perinone did not occur. Instead a deprotonation reaction involving the exocyclic methylene was observed and the corresponding [Ru(eta6-arene)(eta3-IP)Cl] complex was isolated in moderate yields. Mechanistic studies revealed that the base-promoted isomerization of itaco-perinone to citraco-perinone prevented higher yields in the synthesis of the allylic complexes. Additionally, it was observed that IP can dimerize through the exocyclic methylene group, indicating high reactivity of this carbon?carbon double bond. Electronic absorption and emission properties of the perinones and organometallic compounds were studied.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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2,2?-Dipyridylamine (dpa) derivatives carrying a thiol-targeted maleimide group located at the end of an alkyl substituent on the central amine were synthesized. Reaction with the organometallic precursors [(eta6-arene)RuCl2]2 (arene = benzene or p-cymene) yielded the half-sandwich cationic complexes [(eta6-arene)Ru(dpa)Cl]+ where the dipyridylamine derivatives were coordinated as bidentate N,N donor ligands. Enzymatic studies showed that these derivatives were able to inactivate the cysteine endoproteinase papain by S-alkylation of the cysteine active site.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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This work describes the synthesis of a series of Ru(II)-Arene (Arene=p-cymene, benzene) complexes using different N-substituted tetrazole ligands and their PTA analogues. All the complexes have been characterized thoroughly using different analytical techniques. Antiproliferative activity of the synthesized complexes against different cell lines indicates remarkable activity of certain complexes up to nanomolar level. In few cases introduction of water soluble PTA (PTA = 1,3,5- triaza-7-phospha-tricyclo-[3.3.1.1]decane) ligand induce significant cytotoxic activity in the ruthenium complex with respect to their chloro analogues, particularly against Jurkat and MCF-7 cell lines. Interaction with different biomolecules and stability of the RAPTA complexes have been explored in pseudo-pharmacological conditions.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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A new labile areneruthenium sulfide complex, [(C6H6)3Ru3S2](PF6)2 (1), was prepared and characterized both in solid state and in solution. Light-driven de-coodination of the arene ligands has been demonstrated. Two new polynuclear areneruthenium complexes, [(C6H6)4Ru5S4](PF6)2·2CH3CN (2) and [(C6H6)4Ru4S5](PF6)2·1.25CH3CN·0.5H2O (3), were obtained from 1 and structurally characterized. Redox behaviour of [(C6H6)3Ru3S2](PF6)2 and [Ru5S4(C6H6)4](PF6)2·2CH3CN was studied by cyclic voltammetry and reveals one reversible reduction wave.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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1,4-Bis(phenylthio/seleno methyl)-1,2,3-triazoles (L1-L4) synthesized by a ‘Click’ reaction react with [{(eta6-C6H6)RuCl(mu-Cl)}]2 and NH4PF6 resulting in complexes [(eta6-C6H6)RuClL]PF6 (1-4 for L = L1-L4) in which the ligands coordinate in a bidentate mode through S/Se and N of triazole. The CH2EPh (E = S or Se) attached to nitrogen of triazole remains pendent. Ligands and complexes have been authenticated with multinuclei NMR, IR and HR-MS. Single crystal structures of complexes 1-4 have been solved. The Ru-S and Ru-Se bond lengths (A) are respectively 2.388(2)/2.3902(19) and 2.5007(4)/2.5262(19). The disposition of benzene ring, N, S/Se and Cl around Ru is of a piano stool type. For catalytic oxidation of alcohols [Oppenauer-type and with N-methylmorpholine-N-oxide (NMO)] and transfer hydrogenation (TH) of carbonyl compounds [with 2-propanol and glycerol] all the four complexes have been found efficient. The optimum catalyst loadings (in mol%) are: 0.01 (NMO), 0.1 (Oppenauer), 0.01 (TH with 2-propanol) and 0.5 (TH with glycerol). Interestingly, time profiles (under optimum conditions) of two catalytic oxidations and TH’s are almost similar, suggesting that they are competitive on appropriate catalyst loading. DFT calculations are consistent with somewhat low reactivity of 1 in comparison to those of 2-4.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI