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Cyclopentadienyl ruthenium phosphane and carbene complexes are grafted on the surface of mesoporous SBA-15 molecular sieves through an aminosilane linker. The nature of the support after the grafting is examined by powder XRD, TEM and N2 adsorption/desorption analysis. Elemental analysis, FT-IR, DRIFTS, TG-MS and MAS-NMR studies confirm the successful grafting of the complexes on the surface. The grafted materials are applied for catalytic aldehyde olefination and cyclopropanation. The Royal Society of Chemistry.

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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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Cyclic voltammetric studies on a series of alkynyl complexes (M=Fe or Ru; R=Ph, Bun or But; L=CO or P-donor ligand; R’=H or Me) reveal a one-electron oxidation at a glassy carbon electrode in dichloromethane.The chemical reversibility of the oxidation process is dependent upon all four variables (M, L, R and R’) considered in this investigation.

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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 hexane-2,5-dione bis(thiosemicarbazones) ([CH3?C{= N?NH?C(=S)?NHR}?CH2]2, R = H, L1H2; CH3, L2H2?Me; CH2CH3, L3H2?Et; C6H5, L4H2?Ph) with nickel(II) acetate hydrate in refluxing ethanol gave a series of NiIIN2S2 metalloligands [Ni(L-R)] for the generation of hetero-bimetallic complexes. The reaction of equal mole each of [Ni(L1)], [Ni(L2?Me)], [Ni(L3?Et)], or [Ni(L4?Ph)] with [RuCl2(dmso)4] (dmso = dimethyl sulfoxide) at reflux resulted in isolation of neutral dinuclear ruthenium-nickel complexes [RuCl2{(Ni(L1)}(dmso)2] (1), [RuCl2{(Ni(L2?Me)}(dmso)2] (2), [RuCl2{(Ni(L3?Et)}(dmso)2] (3), and [RuCl2{(Ni(L4?Ph)}(dmso)2] (4). Interaction of [Ni(L-R)] with [CpRu(PPh3)2Cl] (Cp? = cyclopentadienyl) at room temperature led to formation of cationic dinuclear organoruthenium-nickel complexes [CpRu{(Ni(L1)}(PPh3)]Cl (5), [CpRu{(Ni(L2?Me)}(PPh3)]Cl (6), [CpRu{(Ni(L3?Et}(PPh3)]Cl (7), and [CpRu{(Ni(L4?Ph}(PPh3)]Cl (8). New bimetallic ruthenium-nickel complexes 1?8 have been characterized spectroscopically, of which molecular structures of three complexes [RuCl2{(Ni(L2?Me)}(dmso)2]¡¤CH2Cl2 (2¡¤CH2Cl2), [CpRu{(Ni(L2?Me)}(PPh3)]Cl?EtOH (6?EtOH), and [CpRu{(Ni(L3?Et}(PPh3)]Cl (7?H2O) have been established by single-crystal X-ray crystallography. Their catalytic activities for the acetalation of benzaldehyde in the presence of molecular H2 have been also investigated in this paper.

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

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This work reports the first method for the synthesis of alpha-hydroxyphosphonates from aldehydes catalyzed by cyclopentadienyl ruthenium(II) complexes. The best results were obtained using the system HP(O)(OEt)2/[RuClCp(PPh3)2] (5 mol%), affording the alpha-hydroxyphosphonates in good to excellent yields with high chemoselectivity. The catalyst [RuClCp(PPh3)2] can be used for at least 12 catalytic cycles with excellent activity and the reactions were carried out under solvent free conditions. DFT calculations were performed to rationalize the mechanism showing that the barriers associated with the H-phosphonate tautomer, HP(O)(OR)2 are unrealistically high. This led us to propose that the catalyst promotes the tautomerization towards phosphite, P(OH)(OR)2, via P-atom coordination, which accounts for the observed reactivity.

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

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Two new, air-stable BINAP complexes of ruthenium(II), (RCp)Ru(S-(-)-BINAP)Cl (R = H, CH3) have been prepared in good yield from the reaction of (RCp)Ru(PPh3)2Cl with S-(-)-BINAP in refluxing toluene.The structure of the methylcyclopentadienyl analog has been determined by X-ray crystallography.Both complexes have been found to be effective homogeneous catalysts for the enantioselective hydrogenation of beta-ketoesters.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
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The rate dependence of the [Ru(eta5-C5H 5)(BIPHOP-F)(acetone)][Y] -catalyzed Diels-Alder reaction of cyclopentadiene with methacrolein on the anion, Y, is shown to be due to selective ion pairing. Pulsed gradient spin-echo (PGSE) diffusion measurements on the model Cp and indenyl complexes [Ru(eta5-C5H 5)(CH2=CH-CN)(BIPHOP-F)][Y], Y = BF4 and BArF, and [Ru(eta5-C9H7)(CH2=CH-CN) (BIPHOP-F)] [Y], Y = BF4 and BArF, respectively, combined with 1H-19F HOESY NMR data can be used to understand how the ion pairing for the BF4 anion differs relative to that of the BArF anion. Solid-state structures for [Ru(eta5-C5H 5)(CH2=CH-CN)(BIPHOP-F)][BF4] and [Ru(eta5-C5H5)(CH2=CH-CN)(BIPHOP- F)][BArF] are reported and support the NMR solution data. The model carbonyl complexes [Ru(eta5-C5H5)(BIPHOP-F)-(CO)][Y], 8 (Y = BF4, SbF6, and BArF) have been synthesized. The IR CO stretching frequencies for 8 showed little variation with anion, thereby proving that the anions do not affect the Lewis acidity of the salts.

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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 bimetallic cyano-bridged [(eta5-C5H 5)(PPh3)2Ru(mu-CN)Ru(PPh3) 2(eta5-C5H5)][PF6] (1) was prepared by reaction of [(eta5-C5H 5)(PPh3)2RuCl] with N,N?-bis(cyanomethyl) ethylenediamine. The single crystal structure determined by X-ray diffraction showed crystallization on the triclinic P1 space group with a perfect alignment of the cyanide bridges. This accentric crystallization was explored having in view the NLO properties at the macroscopic level, determined by the Kurtz Powder technique. Besides the very low efficiency values for the second harmonic generation, the value obtained for the bimetallic complex 1 showed to be higher than one of the parent complex [(eta5-C5H 5)(PPh3)2RuCN] (2).

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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 use of potassium osmate, K2[OsO2(OH)4], as a precursor for some cyclopentadienyl-osmium complexes is described. The X-ray structures of OsBr(PPh3)2Cp, OsCl(dppe)Cp and OsX(dppe)Cp* (X = Cl, Br) are reported.

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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 complex <(OC)4Re(OH2)2>+ reacts with oxalate and squarate to give the complexes <(OC)4Re(OH2)2>C2O4 (1) and <(OC)4Re(OH2)2>C4O4 (2).The reaction of (OC)2(PPh3)2Ru(FBF3)2 with potassium salts of alpha-aminoacids (glycine, L-alanine, L-phenylalanine) yields cationic ruthenium complexes with chelating aminoacidates (3-5).With acetylacetonate the complex <(OC)2(PPh3)2Ru(acac)> (16) is obtained.Nitriles and isonitriles give the complexes <(OC)4Re(N<*>C-R)2> (6: R=Me; 7: R=CH2CO2Et), <(OC)2(PPh3)2Ru(N<*>C-R)2>2 (8: R=Me, 9: R=p-C6H4OMe), <(OC)4Re(C<*>N-R)2> (10: R=(CH2)3Me; 11: R=CH2CO2Et) and <(OC)2(PPh3)2Ru(C<*>N-R)2>2 (12: R=CH2CO2Et; 13: R=C6H11), respectively.With thioethers (OC)4Re(OEt2)FBF3 forms the complexes <(OC)4Re(Ph-S-CH2-S-Ph)> (14) and <(OC)4Re(HO-(CH2)2-S-(CH2)2-S-(CH2)2OH)> (15). Key words: Ruthenium; Rhenium; Phosphorus; Tetrafluoroborate

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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 hydrogenation of myrcene catalyzed by Ru, Cr, Ir and Rh complexes leads to the formation of a complex mixture of mono-, di- and trihydrogenated products. Seven major products have been characterized, showing that they arise from the sigma-alkyl and/or eta3-allyl intermediates formed by the reaction of metal catalysts with both terminal CC bonds of myrcene. A good control of chemoselectivity has been achieved through the appropriate choice of the metal and reaction conditions. Monohydrogenated products have been obtained with excellent combined selectivity of 95-98% at a high conversion of myrcene (>80%). Among the catalysts studied, rhodium complexes show the highest activity and selectivity, especially at temperatures lower than 100 C.

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