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The interionic structure of complexes [Ru(eta6-Arene){(2-R- C6H4)N=C(Me)-C(Me)=N(2-R-C6H4)}-Cl] X was investigated by an integrated experimental (PGSE diffusion and NOE NMR spectroscopy and X-ray single-crystal studies) and theoretical (DFT and ONIOM calculations) approach. PGSE NMR experiments indicated that ion pairing is the main aggregative process in CD2Cl2 and solvents with higher relative permittivity. They also showed that the tendency to ion pairing for isodielectric solvents is higher when the latter are protic. NOE interionic contacts were observed in 2-propanol-d8 even for BARF- salts. Ion pairing was favored by more coordinating counterions and an increase in concentration. An equilibrium between ion pairs and ion quadruples was observed by PGSE measurements in chloroform-d and benzene-d6. Such equilibrium is shifted toward ion quadruples by an increase in the concentration or when least coordinating counterions are used. For small fluorinated counterions, NOE studies located the anion in ion pairs above the plane containing the C=N imine moieties. ONIOM calculations found that this anion-cation orientation was at least 35.9 kJ/mol lower in energy than a second orientation with the anion close to cymene, which, in some cases, was observed in the solid state. NOE investigations on complexes with BPh4 – counterion did not allow a single orientation capable of explaining the observed NOEs to be found. X-ray studies showed that one cation is surrounded by two anions. ONIOM calculations found that these two anion-cation orientations have similar energies. X-ray and NOE NMR data strongly suggest that ion quadruples with BPh4- anions are constituted by an alternation of cations and anions. Interionic NOE intensities are almost invariant on passing from ion pairs to ion quadruples with small fluorinated counterions. X-ray studies suggested at least four possible structures of ion quadruples differing in both disposition and orientation of the ionic moieties. Three structures considered by ONIOM calculations were similar in energy, but more stable than the separated ion pairs.

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

9-Sep-2021 News Final Thoughts on Chemistry for Dichloro(benzene)ruthenium(II) dimer

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We report our third and final investigation into the use of ruthenium based compounds for catalyzing the hydrosilylation of methylvinyldimethoxysilane with methyldimethoxysilane. The catalytic mechanism of dichloro (p-cymene) ruthenium (ii) (B1) is examined and compared to that of previously studied, less active catalysts. Density functional theory (DFT) has been applied to explore the possibility of fine-tuning the catalytic ability of B1.The eta 6-ligand and the sigma-donor ligands were varied to assess the steric and electronic factors that affect the reactivity of the catalyst. The catalytic ability is diminished by increasing the size of the eta 6-ligand (p-cymene replaced by 1,3,5-cyclooctatriene) or the sigma-donor strength of the other ligands (chloride replaced by methyl). The original catalyst (B1) appears to strike an optimum balance with regard to the sigma-donor capabilities of the ligands as it is able to interconvert relatively freely between the Ru(ii) and Ru(iv) oxidation states. All catalytically active compounds benefit from an initial exchange of one of the sigma-donor ligands for a hydride ligand in the induction step. The Royal Society of Chemistry 2009.

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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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Reaction of [RuCl2(eta6-C6H 6)]2 with [10-(CH3)2S-7,8-nido- C2B9H10]- or [9-(CH 3)2S-7,8-nido-C2B9H10] afforded the expected cationic complexes [Ru(eta5-n-(CH 3)2S-7,8-C2B9H10) (eta6-C6H6)]+ (n = 10, (1); 9, (3)), but also the unexpected neutral Ru(eta5-10-HS-7,8-C 2B9H10)(eta6-C6H 6) (2) or Ru(eta5-9-(CH3)S-7,8-C 2B9H10)(eta6-C6H 6) (4) by double and mono demethylation of the (CH3) 2S moiety, respectively.

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

Sep 2021 News Awesome Chemistry Experiments For Dichloro(benzene)ruthenium(II) dimer

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A critical step in creating an artificial photosynthesis system for energy storage is designing catalysts that can thrive in an assembled device. Single-site catalysts have an advantage over bimolecular catalysts because they remain effective when immobilized. Hybrid water oxidation catalysts described here, combining the features of single-site bis-phosphonate catalysts and fast bimolecular bis-carboxylate catalysts, have reached turnover frequencies over 100 s-1, faster than both related catalysts under identical conditions. The new [(bpHc)Ru(L)2] (bpH2cH = 2,2?-bipyridine-6-phosphonic acid-6?-carboxylic acid, L = 4-picoline or isoquinoline) catalysts proceed through a single-site water nucleophilic attack pathway. The pendant phosphonate base mediates O-O bond formation via intramolecular atom-proton transfer with a calculated barrier of only 9.1 kcal/mol. Additionally, the labile carboxylate group allows water to bind early in the catalytic cycle, allowing intramolecular proton-coupled electron transfer to lower the potentials for oxidation steps and catalysis. That a single-site catalyst can be this fast lends credence to the possibility that the oxygen evolving complex adopts a similar mechanism.

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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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Reaction of the ruthenium(IV) chloro-bridged dimer <2> 1 with a range of alkane- and arene-thiols in CH2Cl2 resulted in the formation of the simple, bridge-cleaved adducts (R=Et 2, Me 3, iPr 4, tBu 5 or Ph 6).Reaction of 1 with an excess of thiol in methanol gave doubly thiolate-bridged compounds <2> (R=Et 7, Ph 12 or C6F5 13) each of which exists as two diastereoisomers but as a single geometrical isomer.In the case of 7 and 12 separation of the two diastereomeric forms proved possible because of their remarkably different solubilities in methanol, and their kinetic inertness.Reactions of 2 and 3 with 1 gave the mixed-bridge chloro/thiolato complexes <2(mu-Cl)(mu-SR)> (R=Me 9 or Et 8).The unusual stereochemistry of these compounds is evident from analysis of their variable-temperature 1H NMR spectra.The crystal structure of 8 has been determined.Reaction of 1 with H2S in CH2Cl2 proceeds via the H2S adduct 10, which rapidly reacts with further 1 with accompanying loss of HCl to give the singly SH-bridged complex <2(mu-Cl)(mu-SH)> 11.Reaction of the EtSH compound 2 with a range of Ru(II) and Rh(III)-containing compounds enabled the isolation of a number of unusual mixed-valence and mixed-metal complexes containing one or two bridging ethanethiolate ligands.The ruthenium(IV)-rhodium(III) compounds <(eta3:eta3-C10H16)ClRu(mu-Cl)(mu-SEt)RhCl(eta5-C5Me5)> and <(eta3:eta3-C10H16)ClRu(mu-SEt)2RhCl2(PMe2Ph)2> have been characterized by X-ray crystallography.

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

08/9/2021 News Awesome Chemistry Experiments For Dichloro(benzene)ruthenium(II) dimer

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Polymers of metal complexes of cyclophanes have interest as potential electrical conductors.We now report a general method of synthesis for bis(eta6-<2n>cyclophane)ruthenium(II) derivatives which provides access to model subunits of such polymers.The synthetic sequence involves capping <2n>cyclophanes with arene-ruthenium(II) complexes, removing the arene cap by hydride reduction followed by treatment with acid, and then coupling the (eta6-<2n>cyclophane)ruthenium(II) solvate with another molecule of <2n>cyclophane.In this way bis(eta6-<22>(1,4)cyclophane)ruthenium(II) bis(tetrafluoroborate) (5), bis(eta6-<22>(1,3)cyclophane)ruthenium(II) bis(tetrafluoroborate) (7), bis(eta6-<23>(1,3,5)cyclophane)ruthenium(II) bis(tetrafluoroborate) (8), and (eta6-<22>(1,4)cyclophane(eta6-<22>(1,3)cyclophane)ruthenium(II) bis(tetrafluoroborate) (6) were synthesized.Treatment of 5 with (eta6-<22>(1,4)cyclophane)ruthenium(II) solvate then gave the tris(eta6-<22>(1,4)cyclophane)diruthenium(II) derivative 13, a model subunit of a transition metal-cyclophane polymer.When 5 was treated with (eta6-hexamethylbenzene)ruthenium(II) solvate, an oligomer, 12, having three ruthenium atoms in the chain, formed.The electrochemical behavior of these new complexes has been examined and provides indirect evidence for intervalence electron transfer in the examples having more than one ruthenium atom.Hydride reduction of (eta6-hexamethylbenzene)(eta6-<22>(1,4)cyclophane)ruthenium(II) bis(tetrafluoroborate), 9, gave (eta4-hexamethyl-1,4-cyclohexadiene)(eta6-<22>(1,4)cyclophane)ruthenium(0), 10, whose structure is established by X-ray crystallographic analysis.An analysis of the electronic and 1H NMR spectra of prototype examples of the <2n>cyclophaneruthenium(II) complexes is reported.Treatment of (eta6-hexamethylbenzene)(eta4-<22>(1,4)cyclophane)ruthenium(0) with acid converts the ruthenium-bound, cyclophane-benzene ring to a cyclohexadienyl moiety as present in 26, whose structure is established by X-ray crystallographic analysis.This novel reaction appears to be general as shown by the conversion of (eta6-hexamethylbenzene)(eta4-<24>(1,2,4,5)cyclophane)ruthenium(0), 28, by acid to 29 and the conversion of bis(hexamethylbenzene)ruthenium(0), 30, to 31.Red-Al(Aldrich) reduction of 31 gives a bis(eta5-hexamethylcyclohexadienyl)ruthenium(II) derivative, 32, an analogue of ruthenocene.Similarly, 26 was reduced by Red-Al to 34, a cyclophane-containing bis(cyclohexadienyl) analogue of ruthenocene.

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

08/9/2021 News Extended knowledge of Dichloro(benzene)ruthenium(II) dimer

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By changing the Ru-source, the reaction conditions, and the workup/purification procedure, the batchwise synthesis of a mixed [Ru II(bathophenanthroline)] complex, i.e., of 4b, could substantially be improved (bathophenanthroline = 4,7-diphenyl-1,10-phenanthroline). In addition, we were able to adapt both steps of the synthesis to a microreactor system leading to the desired Ru-complex in a continuous preparation in very high yields. The latter approach is especially suited for an envisaged scale-up.

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

08/9/2021 News New explortion of Dichloro(benzene)ruthenium(II) dimer

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Axial chirality is generated upon complexation of the novel triphos ligand with a metal. In the presence of the diamine dm-dabn, isomerization to the enantiopure triphos-Ru complex was observed. The dm-dabn ligand of the Ru complex exchanges with dpen at room temperature without racemization. dm-dabn = 3,3?-dimethyl-2,2?-diamino-1,1?-binaphthyl, dpen = 1,2-diphenylethylenediamine.

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

08/9/2021 News Some scientific research about Dichloro(benzene)ruthenium(II) dimer

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A series of water-soluble troponate/aminotroponate ruthenium(II)-arene complexes were synthesized, where O,O and N,O chelating troponate/aminotroponate ligands stabilized the piano-stool mononuclear ruthenium-arene complexes. Structural identities for two of the representating complexes were also established by single-crystal X-ray diffraction studies. These newly synthesized troponate/aminotroponate ruthenium-arene complexes enable efficient C-H bond arylation of arylpyridine in water. The unique structure-activity relationship in these complexes is the key to achieve efficient direct C-H bond arylation of arylpyridine. Moreover, the steric bulkiness of the carboxylate additives systematically directs the selectivity toward mono- versus diarylation of arylpyridines. Detailed mechanistic studies were performed using mass-spectral studies including identification of several key cyclometalated intermediates. These studies provided strong support for an initial cycloruthenation driven by carbonate-assisted deprotonation of 2-phenylpyridine, where the relative strength of eta6-arene and the troponate/aminotroponate ligand drives the formation of cyclometalated 2-phenylpyridine Ru-arene species, [(eta6-arene)Ru(kappa2-C,N-phenylpyridine) (OH2)]+ by elimination of troponate/aminotroponate ligands and retaining eta6-arene, while cyclometalated 2-phenylpyridine Ru-troponate/aminotroponate species [(kappa 2-troponate/aminotroponate)Ru(kappa2-C,N-phenylpyridine)(OH2)2] was generated by decoordination of eta6-arene ring during initial C-H bond activation of 2-phenylpyridine. Along with the experimental mass-spectral evidence, density functional theory calculation also supports the formation of such species for these complexes. Subsequently, these cycloruthenated products activate aryl chloride by facile oxidative addition to generate C-H arylated products.

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

8-Sep-2021 News Some scientific research about Dichloro(benzene)ruthenium(II) dimer

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Reaction between trans-Ir(CO)X(PEt3)2 and PF2X (X=Cl) at 193 K gives Ir(CO)X(PEt3)2PF2X, which rearranges at 298 K to form Ir(CO)X2(PEt3)2PF2 (Z).When X=Br or I, product Z is formed at room temperature, but only traces of the intermediate are detected when X=Br, and none at all when X=I.The end-product have been isolated and characterised by NMR and IR spectroscopy and by analysis, and by reactions with O2, S8, Se; with B2H6; with 2 (M=Ru or Os); and with PtCl2(COD).Reaction with H2G (G=O, S, Se) gives Ir(CO)X2(PEt3)2P’FH(G).Crystal structures are reported for Ir(CO)Cl2(PEt3)2P’F2O, for Ir(CO)Cl2(PEt3)2-mu-(P’F2)RuCl2(p-cymene), and for 2PtCl2.In each molecule the angle IrP’Q (Q=O, Ru, Pt) is unusually wide.

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