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The complexes Ru(4,4?-C ? CC6H4C6H4NO2)(PPh3)2(eta-C5H5) and Ru(4,4?-C ? CC6H4C ? CC6H4NO2)(PPh3)2(eta-C5H5) have been prepared and the latter structurally characterized; they belong to a series of organometallic donor-bridge-acceptor compounds containing (cyclopentadienyl)bis(phosphine)ruthenium(II) centres as donors, conjugated arylacetylide bridges, and nitro acceptor groups. Electrochemical data for the series of complexes Ru(C ? CR)(PR?3)2(eta-C5H5) (R=Ph, 4-C6H4NO2, R?=Ph, Me; R=4,4?-C6H4C6H4NO2, (E)-4,4?-C6H4CH=CHC6H4NO2, 4,4?-C6H4C ? CC6H4NO2, 4,4?-C6H4N=CHC6H4NO2, R?=Ph) are consistent with an RuII/III couple whose oxidation potentials vary strongly with chain-lengthening from one-ring to two-ring acetylide ligand, but show little variation with changes at the bridging unit of the two-ring acetylide ligand. The molecular quadratic and cubic optical nonlinearities of the series of complexes have been determined by hyper-Rayleigh scattering (HRS) and Z-scan techniques, respectively. Molecular first hyperpolarizabilities by HRS at 1064 nm are dispersively enhanced; experimental and two-level corrected data suggest an increase in nonlinearity on chain-lengthening of the bridge, in proceeding from C6H4 to C6H4C6H4 and then C6H4C ? CC6H4 and C6H4CH=CHC6H4, a general trend that is reproduced by semiempirical ZINDO computations. Cubic hyperpolarizabilities by Z-scan at 800 nm are negative for complexes with nitro acceptor groups, probably a result of two-photon dispersion, with absolute values (up to 850 × 10-36 esu) large for small organometallic complexes; as with quadratic nonlinearities, cubic nonlinearities increase substantially on bridge lengthening, with little variation on phosphine substitution.

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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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The O-perrhenato complexes LnMOReO3 (LnM = Re(CO)5, Rh(PPh3)2(CO), Ir(PPh3)2(CO), Pt(PPh3)2(H), Ru(eta5-C5H5)(PPh3)2, Os(PPh3)3(CO)(H), Ir(PPh3)2(CO)(H)(Cl) have been prepared from the corresponding halogeno compounds with AgReO4 or NaReO4, respectively.The spectroscopic data (IR, 1H NMR) indicate that ReO4- is a stronger ligand compared to ClO4-, SO3CF3- and BF4-.

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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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The reaction of [(arene)MCl2]2 with pyridylpyrazolyl ligands (L1 and L2) in the presence of ammonium hexafluorophosphate leads to formation of cationic complexes having the general formula [(arene)M(L)Cl]PF6 {M = Ru, arene = p-cymene (1, 4); Cp*, M = Rh (2, 5); Cp*, M = Ir (3, 6); L = 2-(1H-pyrazol-1-yl)pyridine (L1), 2-(3,5-dimethyl-1H-pyrazol-1-yl)pyridine (L2)}. Similarly the reaction of [CpRu(PPh3)2Cl] and [(ind)Ru(PPh3)2Cl] (ind = eta5-C9H7) with L1 and L2 yielded cationic complexes which have been formulated as [(Cp/ind)Ru(L)PPh3]PF6 (7?10). All these complexes were characterized by analytical and spectroscopic techniques. The pyridylpyrazolyl ligands coordinated metal through pyridyl and pyrazolyl nitrogens forming a six-membered metallacycle. The ligands as well as the complexes were evaluated for their in vitro antibacterial activity by agar well diffusion method against two Gram negative bacteria (Escherichia coli and Pseudomonas aeruginosa) and two Gram positive bacteria (Staphylococcus aureus and Bacillus thuriengiensis). Results show that the ligands and the complexes have significant antibacterial activity against Gram negative bacteria. (Figure presented.).

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

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The electrochemical oxidation of methanol was carried out using a series of dppm-bridged Ru/Pd, Ru/Pt and Ru/Au heterobimetallic complexes as catalysts. The major oxidation products were formaldehyde dimethyl acetal (dimethoxymethane, DMM) and methyl formate (MF). The Ru/Pd and Ru/Pt bimetallic catalysts generally afforded lower product ratios of DMM/MF and higher current efficiencies than the Ru/Au catalysts. The Ru/Au bimetallics exhibited product ratios and current efficiencies similar to those obtained from the Ru mononuclear compound CpRu(PPh3)2Cl.Increasing the methanol concentration afforded higher current efficiencies, while the addition of water to the samples shifted the product distribution toward the more highly oxidized product, MF.

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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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Terminal metal acetylide complexes trans-[(dppm)2(Cl)Os(-CC-R-CC-H)] (dppm=Ph2PCH2PPh2, R=-p-C6H4- (1), -p-C6H4-C6H4-p- (2)) and trans-[(Et3P)2(Ph)Pt(CC-p-C6H4-CCH)] (3) have been synthesised by the application of established synthetic routes. Acetylide bridged mixed-metal complexes trans-[(dppm)2(Cl)Os-CC-p-C6H 4-CC-Ru(Cl)(dppm)2] (4), trans-[(Et3P)2(Ph)Pt-CC-p-C6H 4-CC-Ru(Cl)(dppm)2] (5), trans-[(Et3P)2(Ph)Pt-CC-p-C6H 4-CC-Ru(Ph3P)2(eta5-C 5H5)] (6) and trans-[(Et3P)2(Ph)Pt-CC-p-C6H 4-CC-Ru(Ph3P)2(eta5-C 5H4-CH3)] (7) have been formed by the reaction of 1, 2 and 3 with the appropriate metal chlorides. Complex 6 is less soluble in common organic solvents than the other complexes but this insolubility has been overcome by introducing a methylcyclopentadienyl group on the ruthenium centre to form complex 7. Complexes 1, 2, 4, 6 and 7 have shown reversible redox chemistry and in the di-metallic complexes, intramolecular electronic communication has been investigated by cyclic voltammetry. The shift in the lowest energy band in the UV-vis spectra of the mixed-metal complexes 4, 5, 6 and 7 is largely dependent on the various metal fragments.

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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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Allyl thioether complexes [CpRu(P-P)(SRR?)]PF6 (P-P = Ph2PCH2PPh2 (dppm), Ph2PC2H4PPh2 (dppe), R = Me, Et, Ph, R? = 3-propenyl, 3-cyclohexenyl, 2-methyl-2-buten4-yl) and [CpRu(chir)(SRR?)]PF6 (chir = (S,S)-Ph2PCHMeCHMePPh2, R = Me, CH2Ph, R? = 2-methyl-2-buten-4-yl) are obtained from the corresponding thiolate complexes by reaction with the appropriate allyl bromide. Careful oxidation with dimethyldioxirane (DMD) gave the allyl sulfoxide complexes [CpRu(P-P)(MeS(O)CH2CH=CH2)]PF6 (P-P = dppm, dppe). Double oxidation to the corresponding sulfinylmethyl epoxide complexes can be readily achieved with an excess of DMD. Oxidation of the chir complexes proceeds with only moderate diastereoselectivity. The structure of the (R, R/S, S) diastereomer of [CpRu(dppm)(MeS(O)CH2CHCH2O)]PF6 was determined: monoclinic space group P21/c (No. 14), a = 11.21(2), b = 16.762(9), c = 18.45(4) A, beta = 94.4(1), Z = 4. For a representative example, the decomplexation of the sulfoxide-epoxide ligand by sodium iodide in acetone was demonstrated.

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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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[CpRu(dppf)Cl] (Cp=eta5-C5H5) (1) and [(HMB)Ru(dppf)Cl]PF6 ((HMB)=eta6-C6Me6) (3) react with different donor ligands to give rise to N-, P- and S-bonded complexes. The stoichiometric reactions of 1 and 3 with NaNCS give the mononuclear complexes [CpRu(dppf)(NCS)] (2) and [(HMB)Ru(dppf)(NCS)]PF6 (4), respectively, in yields above 80%, while 3 also gives a dppf-bridged diruthenium complex [(HMB)Ru(NCS)2]2 (mu-dppf) (5) in 67% yield from reaction with four molar equivalents of NaNCS. Compound 5 is also obtained in 70% yield from the reaction of 4 with excess NaNCS. With CH3CN in the presence of salts, both 1 and 3 give their analogous solvento derivatives [CpRu(dppf) (CH3CN)] BPh4 (6) and [(HMB)Ru(dppf) (CH3CN)] (PF6)2 (7). With phosphines, the reaction of 1 gives chloro-displaced complexes [(CpRu(dppf)L]PF6 (L =PMe3 (8), PMe2Ph(9), whereas the reaction of 3 with PMe2Ph leads to substitution of dppf, giving [(HMB)Ru(PMe2Ph)2Cl] PF6 (10). The reaction of 1 with NaS2CNEt2 gives a dinuclear dppf-bridged complex [{CpRu(S2CNEt2)} 2(mu-dppf)] (11), whereas that of 3 results in loss of the HMB ligand giving a mononuclear complex [Ru(dppf) (S2CNEt2)2] (12). With elemental sulfur S8, 1 is oxidized to give a dinuclear CpRuIII dppf-chelated complex [{CpRu(dppf)}2(mu-S2)] (BPh4)Cl (13), whereas 3 undergoes oxidation at the ligand, giving a dppf-displaced complex [(HMB)Ru(CH3CN)2Cl] PF6 (14) and free dppfS2. The structures of 1, 2, 5-9, 11, 13 and 14 were established by X-ray single crystal diffraction analyses. Of these, 5 and 11 both contain a dppf-bridge between RuII centers, while 13 is a dinuclear CpRuIII disulfide-bridged complex; all the others are mononuclear. All complexes obtained were also spectroscopically characterized.

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

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Treatment of the trinuclear complex trans-[Pt(CN)2{CN-Fe(dppe)Cp}2] with Cp(dppe)Fe(MeCN)Br or Cp(PPh3)2RuCl leads to the tetranuclear complexes [Pt(CN){CN-Fe(dppe)Cp}3](SbF6) (3) and [Pt(CN){CN-Fe(dppe)Cp}2{CN-Ru(PPh3) 2Cp}](SbF6) (4), containing a T-shaped Pt(CN-Fe)3 or Pt(CN-Fe)2(CN-Ru) skeleton. The electronic communication between the iron and/or ruthenium centers in these complexes was probed by cyclic voltammetry and UV-vis/NIR spectroscopy. Just like in the corresponding trinuclear Pt(CN-M)2 complexes, there is electronic interaction along the linear M-CN chains containing trans-configured platinum, but not along the bent chains containing cis-configured platinum.

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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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The generation of polynuclear complexes with one, two, or four acetylenedithiolate bridging units via the isolation of eta2-alkyne complexes of acetylenedithiolate K[Tp?M(CO)(L)(C2S 2)] (Tp? = hydrotris(3,5-dimethylpyrazolyl)borate, M = W, L = CO (K-3a), M = Mo, L = CNC6H3Me2 (K-3b)) is reported. The strong electronic cooperation of Ru and W in the heterobimetallic complexes [(eta5-C5H5)(PPh 3)Ru(Sa)] (4a) and [eta5-C5H 5)(Me2C6H3NC)Ru(3a)] (4b) has been elucidated by correlation of the NMR, IR, UV-vis, and EPR-spectroscopic properties of the redox couples 4a/4a+ and 4b/4b+ with results from density functional calculations. Treatment of M(II) (M = Ni, Pd, R) with K-3a and K-3b afforded the homoleptic bis complexes [M(3a)2] (M = Ni (5a), Pd (5b), Pt (5c)), and [M(3b)2] (M = Pd (6a) and R (6b)), in which the metalla-acetylendithiolates exclusively serve as S,S?-chelate ligands. The vibrational and electronic spectra as well as the cyclic voltammetry behavior of all the complexes are compared. The structural analogy of 5a/5b/5c and 6a/6b with dithiolene complexes is only partly reflected in the electronic structures. The very intense visible absorptions involve essential d orbital contributions of the central metal, while the redox activity is primarily attributed to the alkyne complex moiety. Accordingly, stoichiometric reduction of 5a/5b/5c yields paramagnetic complex anions with electron-rich alkyne complex moieties being indistinguishable in the IR time scale. K-3a forms with Cu(I) the octanuclear cluster [Cu(3a)] 4 (7) exhibiting a Cu4(S2C2) 4W4 core. The nonchelating bridging mode of the metalla-acetylenedithiolate 3a- in 7 is recognized by a high-field shift of the alkyne carbon atoms in the 13C NMR spectrum. X-ray diffraction studies of K[Tp?(CO)(Me3CNC)Mo(eta2- C2S2)] (K-3c), 4b, 6a, 6b, and 7 are included. Comparison of the molecular structures of K-3c and 7 on the one hand with 4b and 6a/6b on the other reveals that the small bend-back angles in the latter are a direct consequence of the chelate ring formation.

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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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Cationic ruthenium and iron complexes [CpM(PP)]+ (Cp=eta5-C5H5; M=Ru and Fe; PP=Ph 2PCH2CH2PPh2, 2PPh3) can affect vinylidene rearrangement of general internal alkynes via the 1,2-migration of aryl and alkyl groups. Judging from the migratory aptitude of substituted aryl groups, the present reaction is viewed as an uncommon electrophilic rearrangement. Copyright

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