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Thermal and metal-catalyzed cyclization of 1-substituted 3,5-dien-1-ynes via a [1,7]-hydrogen shift: Development of a tandem aldol condensation- dehydration and aromatization catalysis between 3-en-1-yn-5-al units and cyclic ketones

This work investigates the feasibility of thermal and catalytic cyclization of 6,6-disubstituted 3,5-dien-1-ynes via a 1,7-hydrogen shift. Our strategy began with an understanding of a structural correlation of 3,5-dien-1-ynes with their thermal cyclization efficiency. Thermal cyclization proceeded only with 3,5-dien-1-ynes bearing an electron-withdrawing C(1)-phenyl or C(6)-carbonyl substituent, but the efficiencies were generally low (20-40% yields). On the basis of this structure-activity relationship, we conclude that such a [1,7]-hydrogen shift is characterized by a “protonic” hydrogen shift, which should be catalyzed by pi-alkyne activators. We prepared various 6,6-disubstituted 3,5-dien-1-ynes bearing either a phenyl or a carbonyl group, and we found their thermal cyclizations to be greatly enhanced by RuCl 3, PtCl2, and TpRuPPh3(CH3CN) 2PF6 catalysts to confirm our hypothesis: the C(7)-H acidity of 3,5-dien-1-ynes is crucial for thermal cyclization. To achieve the atom economy, we have developed a tandem aldol condensation-dehydration and aromatization catalysis between cycloalkanones and special 3-en-1-yn-5-als using the weakly acidic catalyst CpRu(PPh3)2Cl, which provided complex 1-indanones and alpha-tetralones with yields exceeding 65% in most cases. The deuterium-labeling experiments reveal two operable pathways for the metal-catalyzed [1,7]-hydrogen shift of 3,5-dien-1-ynes. Formation of alpha-tetralones d4-56 arises from a concerted [1,7]-hydrogen shift, whereas benzene derivative d4-9 proceeds through a proton dissociation and reprotonation process.

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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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Spectral, structural and DFT studies of platinum group metal 3,6-bis(2-pyridyl)-4-phenylpyridazine complexes and their ligand bonding modes

Reactions of 3,6-bis(2-pyridyl)-4-phenylpyridazine (Lph) with [(eta6-arene)Ru(mu-Cl)Cl]2 (arene = C6H6, p-iPrC6H4Me and C6Me6), [(eta5-C5Me5)M(mu-Cl)Cl]2, (M = Rh and Ir) and [(eta5-Cp)Ru(PPh3)2Cl] (Cp = C5H5, C5Me5 and C9H7) afford mononuclear complexes of the type [(eta6-arene)Ru(Lph)Cl]PF6, [(eta5-C5Me5)M(Lph)Cl]PF6 and [(Cp)Ru(Lph)(PPh3)]PF6 with different structural motifs depending on the pi-acidity of the ligand, electronic properties of the central metal atom and nature of the co-ligands. Complexes [(eta6-C6H6)Ru(Lph)Cl]PF6 1, [(eta6-p-iPrC6H4Me)Ru(Lph)Cl]PF6 2, [(eta5-C5Me5)Ir(Lph)Cl]PF6 5, [(eta5-Cp)Ru(PPh3)(Lph)]PF6, (Cp = C5H5, 6; C5Me5, 7; C9H7, 8) show the type-A binding mode (see text), while complexes [(eta6-C6Me6)Ru(Lph)Cl]PF6 3 and [(eta5-C5Me5)Rh(Lph)Cl]PF6 4 show the type-B binding mode (see text). These differences reflect the more electron-rich character of the [(eta6-C6Me6)Ru(mu-Cl)Cl]2 and [(eta5-C5Me5)Rh(mu-Cl)Cl]2 complexes compared to the other starting precursor complexes. Binding modes of the ligand Lph are determined by 1H NMR spectroscopy, single-crystal X-ray analysis as well as evidence obtained from the solid-state structures and corroborated by density functional theory calculations. From the systems studied here, it is concluded that the electron density on the central metal atom of these complexes plays an important role in deciding the ligand binding sites.

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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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(Acetonitrile-N)(eta 5-cyclopentadienyl)bis(triphenylphosphine-P)ruthenium(II) tetrafluoroborate

The title compound, [Ru(C5H5)(CH3CN){(C6H 5)3P}2]-BF4, crystallizes with C1 local point group symmetry. The Ru-P distances are 2.343 (1) and 2.365 (1) A, and the Ru-N-C angle is 169.8(5).

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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 new optically pure half-sandwich Cp-Ru diphosphine complex with a chiral metal centre, (S)-Ru(eta5-C5H5)-(EPHOS)Cl {EPHOS is (+)-(1R,2S)-2-[(diphenylphosphino)methylamino]-1-phenylpropyl diphenylphosphinite}

The crystal structure of the compound chloro(eta5-cyclopentadienyl){(1R,2S)-2-[(diphenylphospino) methylamino]-1-phenylpropyl diphenylphosphinite-kappa2P, P?}ruthenium(II), [Ru(C5H5)Cl(C34H33NOP2 ))] was discussed. The pseudo-octahedral complex was found to be chiral and the configuration at the Ru atom was S. The analysis showed that the seven-membered metallacycle adopts a boat-like conformation.

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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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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, Formula: C38H34Cl2O2P2Ru

METHANOL AS A HYDROGEN DONOR IN REACTIONS HOMOGENEOUSLY CATALYSED BY RUTHENIUM AND RHODIUM COMPLEXES

Under suitable conditions methanol can act as a hydrogen donor towards organic substrates, especially for the reduction of ketones to alcohols.A variety of complexes of rhodium, iridium, ruthenium, and osmium have been shown to be active for this reaction; the highest activity observed so far is that of t-phosphine-ruthenium-chloride systems such as .In all the reactions the methanol is oxidised to methyl formate; some carbon dioxide is also formed.Cyclohexanone is reduced to cyclohexanol, methyl vinyl ketone and mesityl oxide to the corresponding saturated ketones, and 4-t-butylcyclohexanone to a 4/1 mixture of the trans and cis 4-t-butylcyclohexanols; aldehydes are reduced with more difficulty and cyclohexene is comparatively unreactive.Possible mechanisms for the reaction are discussed in the light of observations of changes in the catalyst precursors that take place during the rections.The reactions with methanol are also contrasted with those in wich ethanol is used as hydrogen donor.

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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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Transition metal alkynyl complexes by transmetallation from Au(CXiCAr)(PPh3) (Ar = C6H5 or C 6H4Me-4)

Facile acetylide transfer reactions take place between gold(i) complexes Au(CXiCAr)(PPh3) (Ar = C6H5 or C 6H4Me-4) and a variety of representative inorganic and organometallic complexes MXLn (M = metal, X = halide, Ln = supporting ligands) featuring metals from groups 8-11, to afford the corresponding metal-alkynyl complexes M(CXiCR)Ln in modest to good yield. Reaction products have been characterised by spectroscopic methods, and molecular structure determinations are reported for Fe(CXiCC6H 4Me-4)(dppe)Cp, Ru(CXiCC6H4Me-4)(dppe) Cp*, Ru(CXiCC6F5)(eta2-O 2)(PPh3)Cp*, Ir(CXiCC6H 4Me-4)(eta2-O2)(CO)(PPh3) 2, Ni(CXiCC6H4Me-4)(PPh3)Cp and trans-Pt(CXiCAr)2L2 (Ar = C6H5, L = PPh3; Ar = C6H4Me-4, L = PPh3, PMe3). The Royal Society of Chemistry 2009.

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

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Nucleophilic substitution on a Ru-coordinated Cp ring by a carborane anion

The Cp ring in [RuCl(Cp)(PPh3)2] undergoes an apparent nucleophilic attack by the carbanion carb- (Hcarb = 2-Me-1,2-dlcarba-closo-dodecaborane), to give an H-/carb- exchange process, which is favoured by coordination of the hydride to the ruthenium centre.

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

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92361-49-4, Name is Chloro(pentamethylcyclopentadienyl)bis(triphenylphosphine)ruthenium(II), molecular formula is C46H45ClP2Ru, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 92361-49-4, category: ruthenium-catalysts

New series of platinum group metal complexes bearing eta5- and eta6-cyclichydrocarbons and Schiff base derived from 2-acetylthiazole: Syntheses and structural studies

The mononuclear complexes [(eta6-arene)Ru(ata)Cl]PF6{ata = 2-acetylthiazole azine; arene = C6H6[(1)PF6]; p-iPrC6H4Me [(2)PF6]; C6Me6[(3)PF6]}, [(eta5-C5Me5)M(ata)]PF6{M = Rh [(4)PF6]; Ir [(5)PF6]} and [(eta5-Cp)Ru(PPh3)2Cl] {eta5-Cp = eta5-C5H5[(6)PF6]; eta5-C5Me5(Cp*) [(7)PF6]; eta5-C9H7(indenyl); [(8)PF6]} have been synthesised from the reaction of 2-acetylthiazole azine (ata) and the corresponding dimers [(eta6-arene)Ru(mu-Cl)Cl]2, [(eta5-C5Me5)M(mu-Cl)Cl]2, and [(eta5-Cp)Ru(PPh3)2Cl], respectively. In addition to these complexes a hydrolysed product (9)PF6, was isolated from complex (4)PF6in the process of crystallization. All these complexes are isolated as hexafluorophosphate salts and characterized by IR, NMR, mass spectrometry and UV-Vis spectroscopy. The molecular structures of [2]PF6and [9]PF6have been established by single-crystal X-ray structure analyses.

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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 alpha-phenylethynyl-trans-beta-styryl complexes with isonitriles: hemi-labile alkyne coordination

Treatment of the complex CPh)=CHPh>Cl(CO)(PPh3)2> (1) with one equivalent of CNR (R = tBu, C6H3Me2-2,6) gives CPh)=CHPh>Cl(CNR)(CO)(PPh3)2>.Addition of a further equivalent of isonitrile and PF6 leads to the salts CPh)=(CHPh>Cl(CNR)2(CO)(PPh3)2>PF6 and the mixed species CPh)=CHPh>(CO)(CNtBu)(CNC6H3Me2-2,6)(PPh3)2>PF6.The related CPh)=CHPh>(CNtBu)(CO)2(PPh3)2>PF6 is obtained by successive treatment of with diphenylbutadiyne, hexafluorophosphoric acid and isonitrile or of 1 with carbon monoxide, AgPF6, and CNtBu.

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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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Mononuclear and heterodinuclear transition metal complexes of functionalized phosphines. Crystal and molecular structures of (see abstract)

Transition metal complexes of phosphine ethers (Ph2 H4OCH2OCH3-o and PhP(C6 H4OCH2OCH3-o) 2) and phosphinophenol, Ph2H4OH-o are described. Phosphine ethers react with Group 6 metal carbonyls to form complexes of the type [M(CO)4L2] and [M(CO) 5L] (M = Mo, Cr, W). The reaction of Ph2 H4OCH2 OCH3-o with RuCl3¡¤3H2O gave ruthenium(III) complex, [Ru(Ph2H4O-o) 3] through the elimination of CH3OCH2Cl whereas the reaction with CpRu(PPh3)2Cl resulted in the formation of [CpRu(Ph2H4O-o)PPh3]. Treatment of Ph2H4OCH2 OCH3-o with rhodium(I) derivatives resulted in the formation of complexes with the phosphine exhibiting both mono- and bidentate modes of coordination involving the phosphorus center and the phenolic exygen. The reaction of Ph2H4OCH2 OCH3-o with [PdCl2(COD)] led to the isolation of two mononuclear complexes, [PdCl(Ph2H4O-o) (Ph2H4OH-o)] cocrystallized with phosphonium salt, [Ph2P(CH2OCH3)C6H4 OH-o]Cl and [Pd(Ph2H4O-o)2] as confirmed by X-ray diffraction studies. The former shows extensive hydrogen bonding interactions between the complex and the phosphonium salt. The metalloligand, Cp2Zr(OC6H4 PPh2-o)2 obtained by the reaction of Cp2 ZrCl2 with Ph2H4OH-o form heterobimetallic complexes with Mo(0), Re(I) and Ni(0) carbonyl derivatives. The reactions of Cp2Zr(OC6 H4PPh2-o)2 with metal halides such as M(COD)Cl2(M = Pd, Pt) and CpRuCl(PPh3)2 afforded metallacycles, [M(Ph2H4O-o)2] and [CpRu(PPh2C6H4 OH-o)(PPh2 C6H4O-o)], respectively via transmetallation.

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