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Conventional reactions of trans-Ru(CCCCH)2(dppe)2 1 with RuCl(PP)Cp? or AuCl(PPh3) have given the complexes trans-Ru(CCCCR)(CCCCR?)(dppe)2 [R = H, Ru(PP)Cp?, Au(PPh3); R? = Ru(PP)Cp?, (PP)Cp? = (PPh 3)2Cp, (dppe)Cp, (dppe)Cp (not all combinations)]. The Au(PPh3) derivatives react with Co(mu3-CBr)(mu-dppm) (CO)7 to give trans-Ru(CCCCH){CCCCC[Co3(mu-dppm)(CO) 7]}(dppe)2 and trans-Ru{CCCCC[Co3(mu-dppm) (CO)7]}2(dppe)2, which contain respectively four- and five-carbon and two five-carbon chains linking the metal centres. Also described is the addition of tcne to trans-Ru(CCCCH)2(dppe) 2 to give the bis(eta1-tetracyanobutadienyl) complex trans-Ru{CCC[C(CN)2]CHC(CN)2}2(dppe) 2 11, of which the single crystal X-ray structure is reported.

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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 mononuclear chelated complex [RuCl(Cp)(eta2-dppa)] has been synthesised and reacted with [Rh2Cl2(CO)4] to form the heterobimetallic complex [(Cp)Ru(mu-CO)2{(mu-Ph2PN(H)PPh2}RhCl 2]. Complexes of [RuCl(Cp){(PPh2)2CHCH2PPh2}] have been reacted with [Rh2Cl2(CO)4] or [RhCl(CO)2(p-toluidene)]. Characterisation of these new ruthenium complexes was carried out using 31P-NMR, FAB mass spectroscopy, elemental analysis and IR spectrophotometry.

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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 between primary amines (RNH2) and diaryl diazomethanes (Ar2CN2) in the presence of catalytic amounts of the complex [RuCl(eta5-C5H5)(PPh3) 2] (1), in chloroform at 60C, generally affords mixtures of imines Ar2C=NR as main product and amines Ar2CHNHR. Whereas Ar2CHNHR are formed by the expected carbene insertion into the N-H bond of the substrate, the generation of Ar2C=NR is unprecedented. The carbene intermediate [RuCl(=CAr2)(eta5-C5H5)(PPh 3)] seems to be the key-species involved in the formation of both products.

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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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Five ruthenium(II) complexes of the type (eta5-C5H5)Ru(PPh3)(beta-diket) have been synthesised.The structure of these chelated beta-diketonates is assigned from IR and PMR spectral data.A tetrahedral geometry around ruthenium has been suggested for these complexes, similar to that of the starting compound (eta5-C5H5)Ru(PPh3)2Cl.

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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 between RuCl(PPh3)2(eta-C5H5) and LiC6H4Me-p afforded Ru(C6H4Me-p)(PPh3)2(eta-C5H5)(76percent), structurally characterized by a single-crystal X-ray study at c. 295K.Crystals are triclinic, P<*>, a 16.607(4), b 11.397(3), c 11.076(5) Angstroem, alpha 94.90(3), beta 99.52(3), gamma 90.43(2) deg, Z 2; R was 0.036 for 6246 ‘observed’ diffractometer reflections.The p-tolyl molety is ?-bonded to the ruthenium with an Ru-C bond length of 2.122(3) Angstroem.This value is compared with others found for Ru-C(spn) bonds (n = 1-3) in ?-bond complexes; these range from 2.013(6) to 2.18 Angstroem.

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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 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, Recommanded Product: Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

The complexes LnM-CN-Ag-CN with LnM=Cp(dppe)Fe or Cp(PPh3)2Ru are available from [Ag(CN)2]- and [LnM]+ or LnM-CN. They are precursors of [LnM-CN-Ag-NC-MLn]+. Likewise the trinuclear complexes [LnM?-CN-Ag-NC-M?Ln]+ with LnM?=(TPA)Cu and cis-(bpy)2FeCN have been prepared. Irrespective of the CN attachment in the starting materials the cyanide-bridged compounds always contain M-CN-Ag arrays, i.e. silver-isocyanide coordination, thereby proving the lability of the silver-cyanide linkage. Electrochemical measurements have shown that there is no electronic communication between the outer metal centers in the trinuclear complexes.

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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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Two ruthenium acetylide complexes [Ru]C?C(C5H 3RN) (1a, R = H; 1b, R = Me; [Ru] = Cp(PPh3) 2Ru) containing 2-pyridyl groups are prepared and their chemical reactivities are explored. Protonation of the ruthenium acetylide complex 1a with HBF4 takes place at both the nitrogen atom and Css, giving the dicationic pyridiniumvinylidene complex {[Ru]=C=C(H)(C5H 4NH)}(BF4)2 (3a). Addition of BF3 to la yields the Lewis acid/base adduct [Ru]OC(C5H4N? BF3) (4a). In the presence of moisture both complexes 3a and 4a in solution transform into the cationic heterocyclic carbene complex {[Ru]=C(O)CH2(C5H4N?BF2)}BF4 (6a), for which the structure is confirmed by X-ray structure determination. The formation of 6a involves the intermediate {[Ru]=C=C(H)(C5H 4N?BF2OH)}BF4 (5a), characterized by spectroscopic methods. DFT calculations show that the Gibbs free energy change of the exothermic transformation of 5a to 6a is -20.59 kcal/mol. N-Alkylation reactions of 1b with two alkyl bromides BrCH2R? (R? = CH=CHCO2Me and CO2Me) yield two pyridiniumacetylide complexes {[Ru]C? C(C5H3MeNCH2R?)} Br (7b, R? = CH=CHCO2Me; 7c, R? = CO2Me, respectively). Complex 7c, characterized by X-ray structure determination, undergoes further protonation to give the pyridiniumvinylidene complex {[Ru]=C=C(H)(C5H4NCH2R?)2+ (8c). Interestingly, the acetylide complex 7b undergoes a C-C coupling reaction of the acetylic Css with the C=C double bond to give the vinylidene complex 9b, characterized also by X-ray structure determination.

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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 enthalpies of reactions of Cp?RuCl(COD) (Cp?=Cp, Cp* COD=cyclooctadiene) with bis(phosphino)amines of the type Ph2PN(R) PPh2(R=Me 1 or R=Ph 2) and the monochalcogen derivatives Ph2PN(Ph)P(E)Ph2(E=S 3 or Se 4) leading to the formation of Cp?RuCl(PNP) and Cp?RuClPNP(E) complexes, respectively, have been measured by anaerobic solution calorimetry in THF at 30C. These reactions are clean and quantitative. The synthesis and characterization of new organoruthenium complexes is reported. Comparisons with enthalpy data in this two related organoruthenium systems and other similar organometallic systems are also presented.

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

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Cationic ruthenium sulfine complexes [CpRu(PR?3)2(O=S=CHR)]PF6 have been obtained by a variety of methods. Oxidation of the thioaldehyde complexes [CpRu(PR?3)2(S=CHR)]PF6 with either 2-tosyl-3-phenyl-oxaziridine (PR?3 = PMe3) or magnesium-monoperoxyphthalate (PR?3 = 1/2 dppm) gave complexes of arylsulfines (R = Ph, 3-C6H4F, 4-C6H4Cl, 4-C6H4OMe) selectively in their thermodynamically less stable E form. Siloxane elimination from the sulfinato complexes [CpRu(PMe3)2(SO2CHRSiMe3)] yielded complexes of aliphatic sulfines, [CpRn(PMe3)2(O=S=CHR)]PF6 (R = H, Me). Treatment of [CpRu(dppm)(SO2CH2R)] with acetyl chloride led to an oxygen redistribution giving complexes of thioaldehydes [CpRu(dppm)(eta2-S=CH2)]PF6 and [CpRu(dppm)(eta1-S=CHR)]PF6 (R = Ph, 4-C6H4Cl). The structure of the latter was determined by X-ray crystallography. The loss of oxygen can be suppressed by performing the acylation-elimination sequence in the presence of poly-(4-vinylpyridine). This provided a selective access to complexes of Z-sulfines, [CpRu(PMe3)2(O=S=CHR)]PF6 (R = Ph, 4-C6H4Cl) and [CpRu(dppm)(O=S=CHR)]PF6 (R = Ph, 4-C6H4Cl, COOEt, Cl). Complexes of the parent sulfine O=S=CH2 were also obtained by SO transfer to the methylene complex [CpRu(PMe3)2(CH2)]PF6 and methylene transfer to the sulfur monoxide complex [Cp*Ru(PMe3)2 (SO)]PF6. Most of the new sulfine complexes exhibit dynamic behaviour in solution, i. e. ligand rotation, ligand inversion, and eta2/etaI hapticity change. O-Alkylation provided the dicationic complex [CpRu(PMe3)2 (EtO-S=CHMe)](PF6)2, and S-oxidation gave the sulfene complexes [(C5R5)Ru(PMe3)2 (O2S=CH2)]PF6 (R = H, Me).

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