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Hydrogenation of beta-N-substituted enaminoesters in the presence of ruthenium catalysts

beta-Aminoesters were prepared in two simple steps from beta-ketoesters derivatives and primary amines under mild conditions. Their hydrogenation was performed at 50 C in the presence of several organometallic catalysts under acidic conditions. The new beta-N-substituted aminoesters were isolated in moderate to good yields.

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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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Extending metal-capped polyynediyl molecular wires by insertion of inorganic metal units

Several symmetric and asymmetric bis(metalla-diynediyl)ruthenium(II) complexes of the general formula trans-{LxRu} C?CC?C{Ru(dppe)2}C?CC?C{RuL? y} (Lx, L?y = (PPh3) 2Cp, (dppe)Cp, (dppe)Cp*), containing Ru(dppe)2 as the central linking group, have been successfully synthesized and characterized spectroscopically. DFT calculations show that their HOMO’s are delocalized over the Ru-C4-Ru-C4-Ru chain, suggesting that there is electronic interaction between the terminal RuLx groups through the C4 chains and the Ru(dppe)2 center. Limited electrochemical measurements reveal that the complexes undergo a series of five stepwise reversible or quasi-reversible oxidation processes.

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

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Atom transfer radical additions with the cationic half-sandwich complex [Cp*Ru(PPh3)2(CH3CN)]OTf

The cationic ruthenium half-sandwich complex [Cp*Ru(PPh 3)2(CH3CN)][OTf] (2) (Cp* = eta5-C5Me5, OTf = SO3CF 3) was synthesized by reduction of [Cp*RuCl2] 2 with zinc in the presence of NaOTf and subsequent reaction with PPh3. When NaOTf was omitted, the corresponding tetrachlorozincate salts were obtained. Complex 2, as well as the salts [Cp*Ru(CH 3CN)3]2[ZnCl4] (3) and [Cp*Ru(PPh3)2-(CH3CN)] 2[ZnCl4] (4), were characterized by single-crystal X-ray analysis. Complex 2 proved to be a potent catalyst for the atom transfer radical addition of CCl4 and CHCl3 to terminal olefins, displaying a performance superior to that of the previously described neutral catalyst [Cp*RuCl(PPh3)2]. For the addition of CHCl3 to styrene, a total turnover number of 890 was achieved. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.

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

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Pyridine- and pyrimidine-2-thiolate complexes of ruthenium

A series of mononuclear ruthenium complexes containing pyridine- and pyrimidine-2-thiolato ligands was prepared and characterized. The new compounds of general formula CpRu(PPh3)(kappa2S,N-SR) (1) (SR = pyridine-2-thiolate (a), pyrimidine-2-thiolate (b)) were prepared directly by reacting the thiolato anions (RS-) with CpRu(PPh3)2Cl. Complexes 1 readily react with NOBF4 or CO in THF at room temperature to give [CpRu(PPh3)(NO)(kappa1S-HSR)][BF4] 2 (2) and CpRu(PPh3)(CO)(kappa1S-SR) (3), respectively. The one-pot reaction of CpRu(PPh3)2Cl, thiolato anions and bis(diphenylphosphino)ethane (dppe) gave CpRu(dppe)(kappa1S-SR) [dppe: Ph2PCH2CH2PPh2 (4)]. The complex salts, [CpRu(PPh3)2(kappa1S-HSR)]BPh 4 (5) are prepared by mixing CpRu(PPh3)2Cl, HSR and NaBPh4 at room temperature. The structures of CpRu(PPh3)(kappa2S,N-Spy) (1a), [CpRu(PPh3)(NO)(kappa1S-HSpy)][BF4] 2 (2a) and CpRu(PPh3)(CO)(kappa1S-Spy) (3a), (py = C5H4N) have been determined.

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

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Spaltung aromatischer und vinylischer C-H-Bindungen durch Cyclopentadienylruthenium(II)-Komplexe

Neopentylruthenium complexes of the type Cp(MenPh3-nP)2RuCH2CMe3 (Cp = C5H5, C5Me5; n = 0-3) react with aromatic C-H bonds in benzene or toluene to give the corresponding phenyl- or tolyl-ruthenium compounds and neopentane.With toluene, a mixture of the m- and p-tolyl complexes is formed.The reactivity of the neopentylruthenium compounds decreases with increasing degree of methyl substitution at the phosphorus atom, and with bidentate phosphane ligands.A permethylated Cp group increases the reactivity. (C5Me5)(Me3P)2RuCH2CMe3 reacts also with the vinylic C-H bond of ethylene to form an (eta2-ethylene)vinylruthenium complex.

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

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Syntheses and reactivity of ruthenium sigma-pyridylacetylides

Ruthenium sigma-acetylides containing a dangling pyridine were synthesized from the reactions of CpRu(L)2Cl (L = PPh3, 1/2 (C5H4PPh2)2Fe) with 4-ethynylpyridine, (E)-1-(4-ethynylphenyl)2-(4-pyridyl)ethylene, or 4-(ethynylphenyl)(4-pyridyl)acetylene in the presence of NH4+PF6- followed by deprotonation with a base. The dangling pyridine can be protonated, methylated, or ligated to tungsten carbonyl fragments. The ruthenium donor to the pyridinium acceptor charge-transfer absorption appears at longer wavelength as the conjugation chain becomes longer. The quadratic hyperpolarizabilities of the methylated derivatives were determined using the hyper Rayleigh scattering method. X-ray analysis was employed to examine the structure of the dinuclear complex Ru(C?CC5H4N{W(CO)4(PPh 3)})(eta2-dppf)(eta5-C5H 5) (dppf = 1,1?-bis(diphenylphosphino)ferrocene).

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

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Synthesis of halfsandwich ruthenium complexes of sulfinic acid esters [1]

A series of halfsandwich ruthenium sulfinato complexes [CpRu(PR?3)2(SO2R)] (R = Me, CH2Ph, C2H4Ph, Ph, 4-C6H4Me; PR?3 = PMe3, 1/2 dppm) with various electronic and steric environments around the ruthenium centre, have been prepared by insertion of SO2 into a ruthenium carbon bond, by a direct ligand exchange reaction, or by oxidation of thiolato complexes with 3-chloroperoxybenzoic acid. The chiral complexes [CpRu(CO)(PPh3)(SO2R)] (R = Me, CH2Ph, Ph) were obtained similarly by oxidation of the corresponding thiolates with magnesium monoperoxyphthalate. Alkylation of the sulfinato complexes with oxonium salts [R?3O]X (R? = Me, Et; X = BF4, PF6) gave ruthenium complexes of sulfinic acid esters, [CpRu(L)(L?)(S(O)(OR?)R)]X in high yields and, for the chiral complexes, up to 82% de. The esters may be detached from the metal by ligand exchange with acetonitrile. Stronger nucleophiles such as I- or SMe- dealkylate the coordinated sulfinic acid esters.

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

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Some reactions of the ruthenium allenylidene complex [Ru(C=C=CPh2)(PPh3)2Cp][PF6] with nucleophiles

Reactions between [Ru(C=C=CPh2)(PPh3)2Cp][PF6] and nucleophilic reagents LiMe, NaOMe, KCN and KC5H5 have given the neutral substituted alkynyl-ruthenium complexes Ru{CCCPh2(Nu)}(PPh3)2Cp. The molecular structures of complexes with Nu=OMe, CN and C5H5 have been determined.

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

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Synthesis, characterization and electrochemistry of cyclopentadienyl phosphine nitrosyl cyanide complexes of ruthenium(II) and osmium(II). Preparation of the dicyano ruthenium(II) complex, <(eta5-C5H5)Ru(PPh3)(CN)2>Na

A series of novel chiral metal centre complexes of the general form, <"cp"M(PPh3)(NO)(CN)>PF6 with “cp” = eta5-C5H5, M = Ru (1); “cp” = eta5-C5H4-Me, M = Ru (2); “cp” = eta5-C5Me5, M = Ru (3) and “cp” = eta5-C5H5, M = Os (4), has been synthesized in 85percent yield from the corresponding bis-phosphine complexes, <"cp"M(PPh3)2CN>, and characterized by NMR (1H; 31P; 13C) and FTIR spectroscopies.Cyclic voltammetry of 1-4 indicates quasi-reversible MI/II redox couples at potentials (vs.KCl(aq) SCE) of E1/2 -0.125, -0.155, -0.30 and -0.315 V, respectively.Near quantitative syntheses of the precursor bis-phosphine cyanide complexes, from the bis-phosphine halides, have been achieved by using methanolic sodium cyanide.The complex <(eta5-C5H5)Ru(PPh3)(CN)2>Na (6) has been synthesized by treating 1 with sodium azide in acetonitrile followed by methanolic sodium cyanide.

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

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A phosphomide based PNP ligand, 2,6-{Ph2PC(O)}2(C5H3N), showing PP, PNP and PNO coordination modes

A new class of PNP pincer ligands, pyridine-2,6-diylbis(diphenylphosphino)methanone, 2,6-{Ph2PC(O)}2(C5H3N) (1) (hereafter referred to as “bis(phosphomide)”), was prepared by the reaction of picolinoyldichloride with diphenylphosphine in the presence of triethylamine. The bis(phosphomide) 1 shows symmetrical PNP, unsymmetrical PNO and simple bidentate PP coordination modes when treated with various transition metal precursors. The reaction between 1 and [Ru(p-cymene)Cl2]2 in a 1 : 1 molar ratio yielded a binuclear complex [Ru2Cl4(NCCH3)(p-cymene){2,6-{Ph2PC(O)}2(C5H3N)}] (2) containing an unsymmetrical PNO pincer cage around one of the ruthenium centers, whereas the second ruthenium is bonded to the other phosphorus atom along with cymene and two chloride atoms. Symmetrical pincer complexes [RuCl(NCCH3)2{2,6-{Ph2PC(O)}2(C5H3N)}](ClO4) (3), [Ru(eta5-C5H5){2,6-{Ph2PC(O)}2(C5H3N)}](OTf) (4) and [RhCl{2,6-{Ph2PC(O)}2(C5H3N)}] (5) were obtained in the respective reactions of 1 with [RuCl(NCCH3)2(p-cymene)](ClO4), [Ru(eta5-C5H5)Cl(PPh3)2] and [Rh(COD)Cl]2. Group 10 metal complexes [NiCl{2,6-{Ph2PC(O)}2(C5H3N)}](BF4) (6), [PdCl{2,6-{Ph2PC(O)}2(C5H3N)}]ClO4 (7) and [PtCl{2,6-{Ph2PC(O)}2(C5H3N)}]ClO4 (8) were obtained by transmetallation reactions of in situ generated AgI salts of 1 with Ni(DME)Cl2 or M(COD)Cl2 (M = Ni, Pd and Pt). The reactions between 1 and CuX or [Cu(NCCH3)4](BF4) produced mononuclear complexes of the type [CuX{2,6-{Ph2PC(O)}2(C5H3N)}] (9, X = Cl; 10, X = Br; 11, X = I), [Cu(NCCH3){Ph2C(O)}2(C5H3N)}](BF4) (12) and [Cu{Ph2C(O)}2(C5H3N)}2](BF4) (13). Similarly, the silver complexes [AgX{2,6-{Ph2PC(O)}2(C5H3N)}] (14, X = ClO4; 15, X = Br) were obtained by the treatment of 1 with AgClO4 or AgBr in 1 : 1 molar ratios. Treatment of 1 with AuCl(SMe2) in 1 : 1 and 1 : 2 molar ratios produced mono- and binuclear complexes, [AuCl{2,6-{Ph2PC(O)}2(C5H3N)}] (16) and [Au2Cl2{2,6-{Ph2PC(O)}2(C5H3N)}] (17), in good yield. The structures of ligand 1 and complexes 2, 5 and 17 were confirmed using single-crystal X-ray diffraction studies. DFT calculations were carried out to gain more insights into the structure and bonding features as well as feasibility of some key chemical transformations.

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