Tag: M.W:700-800

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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.

Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Quality Control of: Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II). In my other articles, you can also check out more blogs about 32993-05-8

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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.14564-35-3, Name is Dichlorodicarbonylbis(triphenylphosphine)ruthenium(II), molecular formula is C38H34Cl2O2P2Ru. In a Article£¬once mentioned of 14564-35-3, COA of Formula: C38H34Cl2O2P2Ru

REACTIONS OF A DICHLOROCARBENE-RUTHENIUM COMPLEX, RuCl2(CCl2)(CO)(PPh3)2

The dichlorocarbene ligand, in the new complex RuCl2(CCl2)(CO)(PPh3)2, readily undergoes substitution reactions in which the integrity of the metal-carbon bond is maintained.Reactions with species H2X (X=O, S, Se) give chalcocarbonyl complexes RuCl2(CX)(CO)(PPh3)2 while RXH (X=O, S) give new carbene complexes RuCl2(CO)(PPh3)2.Ammonia reacts to give a cyanide-containing complex, RuCl(CN)(CO)(NH3)(PPh3)2, and primary amines, an isocyanide complex, or in the case of certain primary diamines cyclic carbene complexes.RuCl2(CNNMe2)(CO)(PPh3)2 is formed in the reaction with N,N-dimethylhydrazine.Secondary amines, R2NH, react to give chloroaminocarbene complexes, RuCl2(CO)(PPh3)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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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

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Study of half-sandwich platinum group metal complexes bearing dpt-NH2 ligand

A quite general approach for the preparation of eta5-and eta6-cyclichydrocarbon platinum group metal complexes is reported. The dinuclear arene ruthenium complexes [(eta6-arene)Ru(mu-Cl)Cl]2 (arene = C6H6, C10H14 and C6Me6) and eta5-pentamethylcyclopentadienyl rhodium and iridium complexes [(eta6-C5Me5)M(mu-Cl)Cl]2 (M = Rh, Ir) react with 2 equiv. of 4-amino-3,5-di-pyridyltriazole (dpt-NH2) in presence of NH4PF6 to afford the corresponding mononuclear complexes of the type [(eta6-arene)Ru(dpt-NH2)Cl]PF6 {arene = C10H14 (1), C6H6 (2) and C6Me6 (3)} and [(eta6-C5Me5)M(dpt-NH2)Cl]PF6 {M = Rh (4), Ir (5)}. However, the mononuclear eta5-cyclopentadienyl analogues such as [(eta5-C5H5)Ru(PPh3)2Cl], [(eta5-C5H5)Os(PPh3)2Br], [(eta5-C5Me5)Ru(PPh3)2Cl] and [(eta5-C9H7)Ru(PPh3)2Cl] complexes react in presence of 1 equiv. of dpt-NH2 and 1 equiv. of NH4PF6 in methanol yielded mononuclear complexes [(eta5-C5H5)Ru(PPh3)(dpt-NH2)]PF6 (6), [(eta5-C5H5)Os(PPh3)(dpt-NH2)]PF6 (7), [(eta5-C5Me5)Ru(PPh3)(dpt-NH2)]PF6 (8) and [(eta5-C9H7)Ru(PPh3)(dpt-NH2)]PF6 (9), respectively. These compounds have been totally characterized by IR, NMR and mass spectrometry. The molecular structures of 4 and 6 have been established by single crystal X-ray diffraction and some of the representative complexes have also been studied by UV-Vis spectroscopy.

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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, reactivity and structure of some mono and binuclear (eta6-p-cymene)ruthenium(II) complexes

Reactions of [{Ru(eta6-C10H14)Cl2}2] (eta6-C10H14=p-cymene H3C-C6H4-CH(CH3)2) with 4-cyanopyridine (referred hereafler as CNPy) in 1:1 and 1:2 molar ratios in dichloromethane yields the binuclear complex [{Ru(eta6-C10H14)Cl2} 2(mu-CNPy)] and the mononuclear complex [Ru(eta6-C10H14)Cl2(CNPy)]. The latter complex further reacts with [{Ru(eta6-C6Me6)Cl2}2] and [Ru(eta5-C5H5)(PPh3) 2Cl] to give 4-cyanopyridine bridged complexes [Cl2(eta6-C10H 14)Ru(mu-CNPy)Ru(mu6-C6Me 6)Cl2] and [Cl2(eta6-C10H 14)Ru(mu-CNPy)Ru(eta5-C5H 5)(PPh3)2]+. The complex [Ru(eta6-C10H14)Cl2(CNPy)] also undergoes metathetical reactions with EPh3 (E=P, As or Sb) to give complexes with the general formulations [Ru(eta6-C10H14)Cl2(EPh 3)], however its reaction with diphenylphosphinomethane (dppm) in a 1:1 ratio gives the mononuclear complex [Ru(eta6-C10H14)Cl2(dppm)] in which the dppm ligand is present in uncommon coordination mode (eta1-dppm). The reaction products have been characterized by microanalyses and spectroscopic studies (IR, 1H-, 13C-, 31P-NMR). The structure of [Ru(eta6-C10H14)Cl2(CNPy)] [a=10.984(1), b=14.052(1), c=12.189(1) A; beta=114.810(1); V=1707.8(4) A3; Dcalc=1.596 g cm-3; monoclinic P21/c; Z=4] and confirmation of uncommon coordination mode of dppm, in [Ru(eta6-C10H14)Cl2(dppm)] [a=11.504(3), b=19.532(3), c=15.942(3) A; beta=96.08(2); V=3562(2) A3; Dcalc=1.446 g cm-3; monoclinic P21/n; Z=4] has been determined by X-ray crystallography.

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