Category: 32993-05-8

Synthetic Route 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

A hybrid terpyridine-based bis(diphenylphosphino)amine ligand, terpy-C6H4N(PPh2)2: synthesis, coordination chemistry and photoluminescence studies

A new terpyridine-diphos hybrid ligand [4?-{p-(Ph2P)2NC6H4}-2,2?:6?2??-terpy] (1) and its RuII, PdII, AuI and ZnII complexes are described. Preliminary studies on absorption and emission properties are also reported.

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

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Structure, dynamic behavior, and catalytic activity of a novel ruthenium cyclopentadienyl complex with a tridentate P,P,O ligand

Reaction of l,2-bis(bis(o-methoxyphenyl)phosphino)ethane (o-MeO-dppe) with [RuClCp(PPh3)2] (1) at 135 C results in the formation of (eta5-cyclopentadienyl)[1-(bis(o-methoxyphenyl)phosphino-kappaP)- 2-((o-methoxyphenyl)(o-phenolato-kappaO)phosphino-kappaP)ethane]ruthenium(II ) ([RuCp(tappe)]; 3), which constitutes the first example of a ruthenium cyclopentadienyl complex with a tridentate P,P,O ligand. The X-ray structure of 3 has been determined to elucidate its solid-state structure, which shows evidence for a CH/pi interaction. An NMR study corroborates this finding, and temperature-dependent 31P and 1H NMR spectra reveal the dynamic behavior of 3 in solution. Complex 3 shows catalytic activity in the isomerization of allylic alcohols to carbonyl compounds.

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

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Trichlorostannyl complexes of Ruthenium(II): Synthesis, structure, reactivity and computational studies

Trichlorostannyl complexes [Ru(SnCl3) (Cp?)L] (2a-c) were prepared by treatment of optically active half-sandwich chlorocomplexes [RuCl(Cp?)L] (1a-c) with an excess of SnCl2.2H2O in ethanol. Treatment of trichlorostannyl complexes 2a-c with NaBH4 afforded trihydridostannyl derivatives [Ru(SnH3) (Cp?)L] (3a-c) in moderated yields. Treatment of 2a-c with MgBrMe gave the trimethylstannyl complexes Ru(SnMe3) (Cp?)L (4a-c). Alkynylstannyl derivatives [Ru{Sn(C?CPh)3}(Cp?)L] (5a-c) were prepared by treatment of trichlorostannyl compounds 2a-c with an excess of LiC?CPh in thf. All the complexes present optical activity. The complexes were characterized spectroscopically and by X-ray crystal structure determination of [RuCl(eta5-C5Me5)L] (1b), [Ru(SnCl3) (eta5-C5Me5)L] (2b), and [Ru(SnCl3) (eta5-C9H7)L] (2c). The influence of different ligands on the Ru?P interaction in several complexes 1a-c, 2a-c and 3a-c was evaluated by DFT calculations. These calculations indicate that [SnCl3]- has a stronger stabilization effect than [Cl]- and the same occurs between ?C9H7 and ?C5Me5. These relative stabilities combined with the distortion energies of the fragments produce a stabilizing effect in the Ru?P bonds of complex 2c that is twice as strong as in the 1b complex.

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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 reactivity of trihydridostannyl complexes of ruthenium and osmium

Trichlorostannyl complexes M(SnCl3)(Tp)L(PPh3) (1, 2) and M(SnCl3)(Cp)L(PPh3) (5, 6) [M = Ru, Os; L = P(OMe)3 (a), P(OEt)3 (b), PPh(OEt)2 (c), PPh3 (d)] were prepared by allowing chloro complexes MCl(Tp)L(PPh3) and MCl(Cp)L(PPh3) to react with an excess of SnCl2 ¡¤ 2H2O in ethanol. Treatment of trichlorostannyl complexes 1, 2, 5, and 6 with NaBH4 in ethanol yielded tin trihydride derivatives M(SnH3)(Tp)L(PPh3) (3, 4) and M(SnH3)(Cp)L(PPh3) (7, 8). Reaction of these complexes with CCl4 gave the trichlorostannyl precursors 1, 2, 5, and 6. Hydridochlorostannyl intermediates Os(SnH2Cl)(Tp)[P(OMe) 3](PPh3) (9a) and Os(SnHCl2)(Tp)[P(OMe) 3](PPh3) (10a) were also obtained. Reaction of trihydridostannyl complexes M(SnH3)(Tp)L(PPh3) (3, 4) with CO2 (1 atm) led to hydridobis(formate) derivatives M[SnH(OC(H)=O]2](Tp)L(PPh3) (11). In contrast, reaction of the related complexes M(SnH3)(Cp)L(PPh3) (7, 8) with CO2 (1 atm) led to the binuclear OH-bridging bis(formate) derivatives [M[Sn{OC(H)=O)2(mu-OH)](Cp)L(PPh3)]2 (12, 13). A reaction path for the formation of 12 and 13, involving the mononuclear tin hydride complex M[SnH(OC(H)=O]2](Cp)L(PPh3), is discussed. The X-ray crystal structure of 12b is reported. Chlorobis(methyl) stannyl Ru(SnClMe2)(Cp)[P(OEt)3](PPh3) (15b) and trimethylstannyl complexes M(SnMe3)(Tp)[P(OMe) 3](PPh3) (14a) and M(SnMe3)(Cp)[P(OEt) 3](PPh3) (16b, 17b) were prepared by allowing trichlorostannyl compounds 1, 2, 5, and 6 to react with MgBrMe in diethyl ether. Trialkynylstannyl derivatives M[Sn(C?CR)3)(Tp)L(PPh 3) (18, 19) and Ru[Sn(C=CR)3)(Cp)[P(OEt) 3](PPh3) (20b) (R = Ph, p-tolyl) were also prepared from the reaction of trichlorostannyl complexes 1, 2, 5, and 6 with Li +(C=CR)- in thf. The complexes were characterized by spectroscopy and by X-ray crystal structure determination of Ru(SnClMe 2)(Cp)[P(OEt)3](PPh3)(15b).

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

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Thiazyl Chloride Complexes of Ruthenium(II)

The compound (NSCl)3 reacts with ruthenium(II) complexes of type (X=Cl, Br, CN, SCN, or SnCl3) an (pip=piperidine) to yield (X=Cl; X’=Cl, Br, CN, SCN, or SnCl3) and , respectively.The complexes have been characterized by elemental analyses, spectroscopic (i.r., 1H n.m.r., u.v.-visible) magnetic susceptibility, and t.l.c. data.

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

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Comparison of Redox Activity between 2-Aminothioether and 2-Aminothiophenol: Redox-Induced Dimerization of 2-Aminothioether via C-C Coupling

Three chemical reactions of two 2-aminothioethers and 2-aminothiophenol with CpRuIICl(PPh3)2 (Cp- = cyclopentadienyl anion), under identical reaction conditions, are reported. While 2-(methylthio)aniline, H2L1 and an analogous substrate, 2-(phenylthio)aniline yielded dicationic dinuclear complexes [(PPh3)CpRuII(L3/L4)RuIICp(PPh3)]Cl2 (where L3 = (4E)-4-(4-imino-3-(methylthio)cyclohexa-2,5-dienylidene)-2-(methylthio)cyclohexa-2,5-dienimine ([1a]Cl2) and L4 = (4E)-4-(4-imino-3-(phenylthio)cyclohexa-2,5-dienylidene)-2-(phenylthio)cyclohexa-2,5-dienimine ([1b]Cl2)), the reaction with 2-aminothiophenol (H2L2) produced a mononuclear complex [(PPh3)CpRuII(L2)]Cl (where L2 = 6-iminocyclohexa-2,4-dienethione) ([2]Cl). All these complexes are obtained in high yields (65%-75%). Formations of the products from the above reactions involve a similar level of oxidation of the respective substrate, although their courses are completely different. A comparison between the above two chemical transformations are scrutinized thoroughly. Characterizations of these complexes were made using a host of physical methods: X-ray crystallography, nuclear magnetic resonance (NMR), cyclic voltammetry, ultraviolet-visible (UV-vis), electron paramagnetic resonance (EPR) spectroscopy, and density functional theory (DFT). The complexes [1a]Cl2 and [1b]Cl2 showed intense metal-to-ligand charge transfer transition in the long wavelength region of the spectrum, at 860 and 895 nm, respectively, and displayed two reversible electron transfer (ET) processes at [1a]2+: -0.28 and -0.52 V; [1b]2+: -0.13 and -0.47 V, along with an irreversible ET process at 0.76 and 0.54 V, respectively. The ET processes at negative potentials are due to successive reductions of the bridging ligand, which are characterized by EPR and UV-vis spectroscopy. The one-electron reduced compound, [1a]+, showed a intraligand charge transfer transition (ILCT) at 1530 nm. The complex [2]+ showed a reversible ET process at -0.36 V and two irreversible ET processes at -1.04 and 1.18 V, respectively. DFT calculations were used to support the spectral and redox properties of the complexes and also to throw light on the difference of redox behavior between thioether and thiophenol substrates. (Chemical Equation Presented).

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

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Half-Sandwich Ruthenium(II) Complexes as Catalysts for Stereoselective Carbene-Carbene Coupling Reactions

Cyclopentadienyl complexes of general formula [RuX(eta5-ligand)(PR3)2] have been found to catalyze the stereoselective decomposition of ethyl diazoacetate (EDA) to form diethyl maleate (DEM) in 95-99% purity with less than 1 mol % of catalyst, at temperatures depending on the bulkiness of the phosphine and the eta5-ligand as well as the nature of the anionic ligand X. A detailed study of the reaction between [RuCl(eta5-C5H5)(PPh3) 2] and EDA suggests that dissociation of one PPh3 is a key step of the catalytic process, which proceeds via the intermediate [RuCl(eta5-C5H5)(=CHCO 2Et)(PPh3)]. Although this electrophilic carbene was not detected in the reaction mixture, it was independently prepared in solution at low temperature starting from [Ru(eta2-02CMe)(eta5-C5H 5)(PPh3). The acetate reacts with EDA at -40C to form the cyclic ester [Ru(CH(CO2Et)OC(Me)O)(eta5-C5H 5)(PPh3), which on treatment with Me2SiCl2 gives the metal carbene postulated in the catalytic cycle. The stoichiometric reaction of the latter compound with EDA selectively affords the olefin derivative [RuCl-(eta5-C5H5)(eta 2-DEM)(PPh3)], which was also detected in the catalytic cycle. The new complexes [RuCl(eta5-C5H5)(PR3)2] (PR3 = PPh2(2-MeC6H4), PPh2Cy, P(3-MeC6H4)3), bearing phosphines bulkier than PPh3, have been prepared in high yield starting from ruthenium trichloride hydrate, cyclopentadiene, and phosphine in refluxing ethanol.

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

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Alkenylvinylidene and allenylidene complexes: Evidence for the formation of a metal-trienylidene intermediate

Reactions of [Ru(thf)(PPh3)2(eta-C5H5)][PF 6] with buta-1,4-diyne in the presence of nucleophiles give alkenylvinylidene or allenylidene complexes; the results are rationalised in terms of the formation of the intermediate trienylidene cation [Ru(C=C=C=CH2)-(PPh3)2(eta-C 5H5)]+ which undergoes nucleophilic addition at Cgamma; the X-ray structure of the heteroallenylidene [Ru{C=C=CMe(NPh2)}(PPh3)2(eta-C 5H5)][PF6] 2 is determined.

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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

Alkynethiolato and alkyneselenolato ruthenium half-sandwich complexes: Synthesis, structures, and reactions with (eta5-C5H5)2Zr

Alkynethiolato and alkyneselenolato complexes of ruthenium, CpRu(PPh3)2(EC?CR) (Cp = eta5-C5H5; E = S, R = Ph (1a), SiMe3 (1b), tBu (1c); E = Se, R = Ph (2a), SiMe3 (2b)), were synthesized by the reactions of CpRuCl-(PPh3)2 with corresponding lithium alkynechalcogenolates in THF. An analogous reaction of Cp*RuCl(PEt3)2 (Cp* = eta5-C5Me5) with LiSC?CPh produced Cp*Ru(PEt3)2(SC?CPh) (3). Complexes 1a and 2a were allowed to react in THF with “Cp2Zr”, generated in situ from CP2ZrCl2 and 2 equiv of n-BuLi, from which the S-bridged Ru-Zr dinuclear complexes CpRu(PPh3)(C?CPh)(mu-S)ZrCp2 (4a) and CpRu(PPh3)(C?CPh)(mu-Se)ZrCp2 (4b) were isolated, respectively. In these complexes, C-S(Se) bond cleavage of the alkynechalcogenolate ligands was promoted by “Cp2Zr”, and the Zr atom was oxidized from II to IV. Treatment of 4a and 4b in THF under 1 atm CO gave rise to CpRu(CO)(C?CPh)(mu-E)ZrCp2 (E = S (5a), Se (5b)), while addition of tert-butyl isocyanide to a THF solution of 4b afforded CpRu(CNtBu)(C?CPh)(mu-Se)ZrCp2 (6). The crystal structures of 1a, 1c, 2a, 2b, 3, 4a, 4b, and 5b were determined by X-ray diffraction analysis.

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Reference£º
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)

Dihydrogen complexes of ruthenium. 2. Kinetic and thermodynamic considerations affecting product distribution

Cationic ruthenium dihydrogen complexes of the form [(eta-C5H5)Ru(L)(L?)(eta2-H 2)]BF4 (L = CO, L? = PCy3 (1a), PPh3 (2a), PMe2Ph (3a), PMe3 (4a) have been prepared by protonation of the corresponding neutral hydrides. Carbonyl free derivatives such as [(eta-C5H5)Ru(P P?)(eta2-H2)]BF4 (P P? = 1,2-bis(dimethylphosphino)ethane (dmpe) (5a), (1,1-dimethyl-2,2-diphenylphosphino)ethane (dmdppe) (6a), (R)-(+)-1,2-bis(diphenylphosphino)propane ((R)-prophos) (8a), bis(PPh3) (9a)) were similarly prepared. Pentamethylcyclopentadienyl analogues [(eta-C5Me5)Ru(P P?(eta2-H2)]BF4 (P P? = dmdppe (7a), (PPh3J2 (10a)) and [(eta-C5Me5)Ru(CO)(PCy3)(eta 2-H2)]BF4 (11a) have also been prepared. Identification of these species as dihydrogen complexes is based upon observation of substantial H-D coupling (22-32 Hz) in the 1H NMR spectra of the HD analogues, prepared by protonation of the corresponding deuterides. In every case studied in detail, the kinetic product of the protonation reaction is the dihydrogen complex, but an intramolecular isomerization occurs to give variable amounts of the transoid dihydride form at equilibrium. The composition of the equilibrium mixture and the rate at which the equilibrium is obtained depend upon the ligand environment. Facile rotation of the coordinated H2 ligand in the ruthenium complexes is established by the study of chiral complexes. The coordinated H2 in these complexes is substantially activated toward heterolytic cleavage. In the case of 5a, the measured pKa is 17.6 (CH3CN), with the dihydrogen form deprotonated more rapidly than the dihydride.

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