Category: 32993-05-8

Electric Literature of 32993-05-8, Catalysts are substances that increase the reaction rate of a chemical reaction without being consumed in the process. 32993-05-8, Name is Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II), molecular formula is C41H35ClP2Ru. In a Article£¬once mentioned of 32993-05-8

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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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

Synthetic Route of 32993-05-8. Chemistry is an experimental science, and the best way to enjoy it and learn about it is performing experiments.Introducing a new discovery about 32993-05-8, Name is Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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

The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.32993-05-8, Name is Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II), molecular formula is C41H35ClP2Ru. In a Article£¬once mentioned of 32993-05-8, COA of Formula: C41H35ClP2Ru

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

Chemistry is an experimental science, and the best way to enjoy it and learn about it is performing experiments.Introducing a new discovery about 32993-05-8, Name is Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II), Application In Synthesis of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II).

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

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A combined QM/MM study of ligand substitution enthalpies in the L2Fe(CO)3, RuCpL2Cl, and RuCp*L2Cl systems

A combined density functional and molecular mechanics approach (QM/MM) has been validated in a study of the substitution reactions: (i) (PH3)2Fe(CO)3 + 2ER3 mutually implies (ER3)2Fe(CO)3 + 2PH3 (ER3 = PMe3, PEt3, PMePh2, PPh3, PCyPh2, P(i)Pr3, PBz3, PCy3, AsEt3, AsPh3); and (ii) Cp’Ru(PH3)2Cl + 2ER3 mutually implies Cp’Ru(ER3)2Cl + 2PH3 (Cp’ = C5H5, C5(CH3)5; ER3 = PMe3, PEt3 P(n)Bu3, PMe2Ph, PMePh2, PPh3, AsEt3, P(OMe)3, P(OPh)3, P(OCH2)3CEt). The steric influence of the R substituents on the substitution enthalpies correlates well with experimental data. The combined QM/MM approach is also able to afford molecular structures in good accord with experimental estimates.

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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 and transition metal complexes of 1,1?-bis(diphenylethynylphosphino)ferrocene

The new ferrocene based bisphosphine [Fe{C5H4P(C[tbnd]CPh)2}2] (1) was synthesized in 82% yield by the treatment of bis(dichlorophosphino)ferrocene [Fe(C5H4PCl2)2] with four equivalents of lithium phenylacetylide. The reactions of 1 with aq. H2O2, elemental sulfur or selenium afforded bis(chalcogenide) derivatives, [Fe{C5H4P(E)(C[tbnd]CPh)2}2] (2 E = O, 3 E = S, 4 E = Se). The reaction of 1 with [M(NC5H11)2(CO)4] (M = Mo, W), [RuCp(PPh3)2Cl] and [M(COD)Cl2] (M = Pd, Pt) resulted in the formation of the respective chelate complexes, [Fe{C5H4P(C[tbnd]CPh)2}2{M(CO)4}] (5 M = Mo, 6 M = W), [Fe{C5H4P(C[tbnd]CPh)2}2{RuCp(Cl)}] (8) and [Fe{C5H4P(C[tbnd]CPh)2}2{MCl2}] (9 M = Pd, 10 M = Pt), whereas the reaction of 1 with [Ru(eta6-p-cymene)Cl2]2 and [AuCl(SMe2)] yielded the corresponding bimetallic complexes [Fe{C5H4P(C[tbnd]CPh)2}2{RuCl2(eta6-p-cymene)}2] (7) and [Fe{C5H4P(C[tbnd]CPh)2}2{AuCl}2] (15). The reactions between 1 and CuX in equimolar ratios also yielded binuclear complexes, [Fe{C5H4P(C[tbnd]CPh)2}2{CuX}2] (11 X = Cl, 12 X = Br, 13 X = I), whereas [Cu(CH3CN)4]BF4 yielded the cationic complex [(Fe{C5H4P(C[tbnd]CPh)2}2)2Cu]BF4 (14). All the compounds were characterized by spectroscopic methods and the structures of complexes 1, 5, 6, 8, 10, 13 and 14 were confirmed by single crystal X-ray diffraction studies.

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

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Cyclopentadienyl-ruthenium and -osmium complexes VII. Formation and properties of ion-pairs containing the dihydride (eta-cyclopentadienyl)bis(triphenylphosphine)-ruthenium(IV) cation

The + cation in the simple and fast reaction of CpRuH(PPh3)2 with organic sulphonic acids in polar solvents (methanol, acetone) has been obtained in the form of ion-pairs.The reaction runs for several minutes, with practically quantitative yields.The dihydride complex cation obtained may be isolated from polar solutions as a sparingly soluble ion-pair with the tetraphenylborate anion.In the ion-pairs a reduction-elimination process slowly proceeds with the formation of non-ionic compounds of the CpRu(sulphonate)(PPh3)2 type.Also, the effect of methyl substituents in the Cp-ring on shifts in the 31P NMR signals and MS(FD) investigations of the new compounds obtained have been described.Explanation of the new group signals in the MS(FD) spectra as originating from the fragments formed, containing two ruthenium atoms ?-bonded to the phenyl ring of BPh4, i.e. +, were proposed.In the case of compounds containing the PPh3 molecule, a similar phenomenon occurs.For fragments obtained in the MS(FD) spectra, the formula + was ascribed.

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