Category: 32993-05-8

32993-05-8, Name is Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II), molecular formula is C41H35ClP2Ru, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 32993-05-8, Recommanded Product: 32993-05-8

Easy hydrolysis of white phosphorus coordinated to ruthenium

The P4 molecule bound to ruthenium as an eta1- ligand in [CpRu(PPh3)2(eta1-P4)]Y (Y = PF6, CF3SO3) undergoes an easy reaction with water in exceedingly mild conditions to yield PH3, which remains coordinated to the [CpRu(PPh3)2] fragment, and oxygenated derivatives. The Royal Society of Chemistry 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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DIASTEREOMERIC CHIRAL DIPHOSPHINE CHLORO(eta5-CYCLOPENTADIENYL)-RUTHENIUM(II) COMPLEXES AND THE CRYSTAL STRUCTURE OF <(S)RuCl(eta5-C5H5)<(R)Ph2PCH(Me)CH2PPh2>>

Diastereomeric > chelate complexes (where R=CH3, cyclo-C6H11, or C6H5) from in nearly equimolar amounts in the displacement reaction of triphenylphosphine form .The diastereomers were separated by fractional crystallization.Diastereomeric composition at the equilibrium showed a low asymmetric induction (28-41percent) by the optically active diphosphine ligand on the chiral ruthenium atom.The absolute configuration at the ruthenium atom has little influence on the chiroptical properties of the complexes, which appear to be dominated, at least in the visible region, by the chiral conformation of the chelate ligand.The crystal structure of the title diastereomer, <(S)RuCl(eta5-C5H5)-<(R)Ph2PCH(Me)CH2PPh2>>, has been investigated.It is monoclinic, space group P21, with a=9.688(3), b=15.037(4), c=10.556(2) Angstroem, beta=113.54(2)deg, and Z=2.The structure was solved by Patterson and Fourier methods, and refined by least squares on the basis of 2 000 significant counter data, to a final R value of 0.042.The complex shows a distored lambda conformation of the diphosphine ligand in the chelate five-membered ring, in the solid state.The Ru-Cl and Ru-P interactions are 2.444(2) and 2.277 Angstroem (mean value), respectively.

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

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Organometallic complexes for nonlinear optics: Part 19. Syntheses and molecular quadratic hyperpolarizabilities of indoanilino-alkynyl-ruthenium complexes

The terminal alkyne 4-HCCC6H4N=CCH=CtBuC(O)CtBu=CH (1) and ruthenium complex derivatives trans-[Ru(CC-4-C6H4N=CCH=CtBuC(O)C tBu=CH}Cl(dppm)2] (2) and [Ru{CC-4-C6H4N=CCH=CtBuC(O)C tBu=CH}(PPh3)2(eta-C5H 5)] (3) have been synthesized. An X-ray structural study of 3 reveals the expected equivalent C-C bond lengths of the phenyl and alternating C-C and C=C bond lengths of the quinonal ring in the indoanilino-alkynyl ligand; there is a dihedral angle of 47.59 between the phenyl and quinonal rings, probably a result of ortho-hydrogen repulsion. Metal-centred oxidation potentials of 2 and 3 are similar to those of ‘extended chain’ 4-nitroaryl-alkynyl complex analogues. Irreversible quinonal ring-centred reductions occur at significantly more negative potentials than the quasi-reversible reductions in their nitro-containing analogues. Quadratic optical nonlinearities by hyper-Rayleigh scattering at 1064 nm for 2 (417¡Á10-30 esu) and 3 (658¡Á10-30 esu) are both large, but resonance enhanced. Two-level-corrected nonlinearities for these complexes (124¡Á10-30, 159¡Á10-30 esu, respectively) are also large, despite the presence of electron-donating tert-butyl groups reducing the efficiency of the (formally) electron-accepting quinonal ring in these donor-bridge-acceptor complexes.

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

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Organometallic ammine complexes: the preparation and X-ray crystal structures of <(eta5-C5H5)Ru(PPh3)2(NH3)>PF6 and <(eta5-C5H5)Ru(PPh3)(CNt-Bu)(NH3)>PF6

Reaction of the neutral chloro-complexes <(eta5-C5H5)Ru(PPh3)2Cl> (1) and <(eta5-C5H5)Ru(PPh3)2)(CNt-Bu)Cl> (2) with ammonium hexafluorophosphate gives the ammonia cations <(eta5-C5H5)Ru(PPh3)2(NH3)>PF6 (3) and <(eta5-C5H5)Ru(PPh3)(CNt-Bu)(NH3)>PF6 (4).The crystal structures of 3 and 4 have been determined, and the 15NH3 isotopomers prepared to facilitate spectroscopic studies.The nature of the product from the reaction of 1 and NH4F in the presence of a halide ion trap has been established.

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

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Organometallic complexes for nonlinear optics. 11.1 molecular quadratic and cubic hyperpolarizabilities of systematically varied (cyclopentadienyl) (triphenylphosphine)nickel sigma-arylacetylides

The complexes Ni(C?CR)(PPh3)(eta-C5H5) (R = 4-C6H4NO2 (3), 4,4?-C6H4C6H4NO2 (4), (E)4,4?-C6H4CH=CHC6H4NO 2 (5), (Z)-4,4?-C6H4CH=CHC6H4NO 2 (6), 4,4?-C6H4C?CC6H4NO 2 (7), 4,4?-C6H4N=CHC6H4NO 2 (8)) have been prepared. Electrochemical data for the series of complexes NiCl(PPh3)(eta-C5H5) (1), Ni(C?CPh)(PPh3)(eta-C5H5) (2), and 3-8 have been determined. Introduction of nitro substituent (in progressing from 2 to 3) results in a substantial increase in the NiII/III oxidation potential, all of which is lost on progressing from a one-ring (3) to two-ring (4-8) chromophore. 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. HRS measurements at 1064 nm are consistent with an increase in beta upon chromophore chain-lengthening (in progressing from 3 to 7 to 5), replacing Z by E stereochemistry (in progressing from 6 to 5), and in replacing N by CH (in progressing from 8 to 5), general trends that are maintained with the two-level-corrected data. Nonlinearities for the 18-electron nickel complexes are larger than those for related 14-electron (triphenylphosphine)gold acetylides, but smaller than those for the more easily oxidizable 18-electron (cyclopentadienyl)bis(phosphine)ruthenium acetylide analogues. Z-scan data at 800 nm reveal a negative gamma for the nitro-containing complexes, consistent with the dispersion effect of two-photon states contributing to the nonlinearities. An increase in gamma upon chromophore chain-lengthening (in progressing from 3 to 5, 4 and 7) and replacing Z by E stereochemistry (in progressing from 6 to 5) is observed. Nonlinearities for the extended-chromophore acetylide complexes 5 and 7 are significantly less than those for the (triphenylphosphine)gold acetylide analogues.

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

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Synthetic, spectral and structural aspects of some mono- and binuclear (homo/hetero) Ru(II) hydrido carbonyl complexes

Reactions of the poly-pyridyl bridging ligand 2,4,6-tris(2-pyridyl)-1,3,5-triazine; 2,3-bis(2-pyridyl)-pyrazine and 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (referred hereafter as tptz, bppz and bptz respectively) with [RuH(CO)Cl(PPh3)3] in methanol, gave highly stable cationic complexes with the formulation [RuH(CO)(PPh3)2(L)]+. Further, the mononuclear complex [RuH(CO)(PPh3)2(bppz)]PF6 reacted with K2PtCl4, [PdCl2(benzonitrile)2], [RuH(CO)(PPh3)2(bppz)PdCl2]PF 6, [RuH(CO)(PPh3)2(bppz)(eta 6-C10 H14)RuCl](PF6) 2, [RuH(CO)(PPh3) 2(bppz)(eta 6-C6Me6)Cl2Ru](PF 6)2, [RuH(CO)(PPh3)2 (bppz)(eta5-C5H5) (PPh 3)Ru](PF6)2 and [RuH(CO)(PPh 3)2(bppz)Rh(eta5-C5 Me5)Cl](PF6)2 in quantitative yield. The reaction products have been characterized by elemental analyses, IR, 1H-, 1H-1H-COSY, 13C-, 31P-NMR, ESMS, FAB mass spectroscopy, electronic spectra and cyclic voltammetry. Molecular structure of the representative mononuclear complex [RuH(CO)(PPh3)2(tptz)]BF4 has been confirmed by X-ray crystallography. Crystal structure determination revealed eta2-coordination of the ligand tptz with the metal center. Crystal data: monoclinic, P21/n, a = 17.810(6) A?, b = 22.233(9) A?, beta = 90.06(3), Z = 4, R = 0.078.

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

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Novel mononuclear eta5-pentamethylcyclopentadienyl complexes of platinum group metals bearing pyrazolylpyridazine ligands: Syntheses and spectral studies

Condensation of 3,6-dichloropyridazine with 3,5-dimethylpyrazole in 1:1 ratio yielded one side substituted pyrazolylpyridazine ligand 3-chloro-6-(3,5-dimethylpyrazolyl)pyridazine (L) while condensation of 3,6-dichloropyridazine with substituted pyrazoles in 1:2 ratio yielded both side substituted pyrazolylpyridazine ligands such as 3,6-bis(pyrazolyl)pyridazine (L1), 3,6-bis(3-methylpyrazolyl)pyridazine (L2) and 3,6-bis(3,5- dimethylpyrazolyl)pyridazine (L3). A new series of cationic mononuclear complexes of the type [(eta5-Cp)Ma(L)(PPh3)]PF6, [(eta5-Cp)Mb(L)Cl]PF6, [(eta5-Cp)Ru(L?)(PPh3)]PF6and [(eta5-Cp)Mb(L?)Cl]+(where Ma= Ru, Os; Mb= Rh, Ir and L? = L1, L2, L3) bearing pyrazolylpyridazine and eta5-cyclopentadienyl ligands are reported. The complexes have been completely characterized by spectral studies. The molecular structures of representative complexes have been determined by single crystal X-ray crystallography.

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

32993-05-8, Name is Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II), molecular formula is C41H35ClP2Ru, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 32993-05-8, Quality Control of: Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

DISUBSTITUTED VINYLIDENE COMPLEXES OF IRON AND RUTHENIUM: NUCLEOPHILIC PROPERTIES OF eta1-ACETYLIDE LIGANDS

The eta1-acetylide complexes (C5H5)ML2(C<*>CR) (M=Fe, Ru; L=PPh3, L2=Ph2PCH2CH2PPh2) are nucleophilic at the beta-carbon and react with a variety of mild electrophiles to yield the corresponding disubstituted vinylidene complexes <(C5H5)ML2(=C=CRR')>PF6.

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

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Reactions of Ruthenium Complexes Containing Pentatetraenylidene Ligand

Two ruthenium acetylide complexes [Ru]?C?C?C?C?C(OR)(C3H5)2 (2, R=H and 2 a, R=CH3; [Ru]=Cp(PPh3)2Ru) each with two cyclopropyl rings were synthesized from TMS?C?C?C?C?C(OH)(C3H5)2 (1; TMS=trimethylsilyl). Treatments of 2 and 2 a with allyl halide in the presence of KPF6 afforded the vinylidene complexes 3 and 3 a, respectively. When NH4PF6 was used, instead of KPF6, additional ring-opening reaction took place on one of the three-membered ring. Treatment of [Ru]Cl with 1,3-butadiyne (6), bearing an epoxide ring, afforded acetylide complex 7 with a furyl ring. Treatment of 2 a with Ph3CPF6 presumably afforded pentatetraenylidene complex {[Ru]=C=C=C=C=C(C3H5)2}[PF6] (10), which was not isolated. Additions of various alcohols in a solution of 10 generated a number of disubstituted allenylidene complexes {[Ru]=C=C=C(OR)?C=C(C3H5)2}[PF6] (11). Treatment of 11 with K2CO3 afforded the acetylide complex 12 bearing a carbonyl group, characterized by single X-ray diffraction analysis. Addition of a primary amine to 10 caused cleavage of the farthermost C=C bond and several allenylidene complexes {[Ru]=C=C=C(Me)(NHR)}[PF6] (18) were isolated.

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

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Reactions of ‘GaI’ with organometallic transition metal halides

Two approaches towards the synthesis of phosphine ligated half-sandwich complexes [(etax-CxHx)M(PR3)2GaI2]n containing diiodogallyl ligands have been investigated. Insertion of ‘GaI’ into the Mo-I bond of (eta7-C7H7)Mo(CO)2I has been shown to yield the crystallographically characterized dimeric complex [(eta7-C7H7)Mo(CO)2GaI2]2 (2). Attempts to substitute the carbonyl ligands by the phosphine ligand dppe [dppe = bis(diphenylphosphino)ethane] have been shown instead to yield the sparingly soluble complex [(eta7-C7H7)Mo(CO)2GaI2]2(mu-dppe) (3) in which the phosphine bridges two [(eta7-C7H7)Mo(CO)2GaI2] units via a pair of P ? Ga donor/acceptor bonds. By contrast, attempts to insert ‘GaI’ directly into the metal-halogen bond of phosphine ligated complexes such as (eta5-C5H5)Ru(PPh3)2Cl or (eta5-C5H5)Ru(dppe)Cl have been shown to result in the formation of the tetraiodogallate species(eta5-C5H5)Ru(PPh3)2(mu-I)GaI3 (5) and [(eta5-C5H5)Ru(dppe)]+[GaI4]- (7).

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