18-Sep News Discovery of Dichlorodicarbonylbis(triphenylphosphine)ruthenium(II)

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To study steric and electronic factors that affect the C-H activation of Schiff bases by the complex [Ru(PPh3)2(CO) 2Cl2], systematic spectroscopic analyses were performed for a family of Ru(II) complexes of type [Ru(PPh3)2(CO)L]. Among eight Schiff bases [H2Ln (n = 1-8)], synthesized by condensation of methyl-4-formyl benzoate with 4-aminoacetophenone, 1-naphthylamine, 2-amino-5-chloropyridine, 8-aminoquinoline, semicarbazide hydrochloride, 2-aminophenol, thiosemicarbazide and 2-aminothiophenol, it was observed that the C-H activation was dependent on the kind as well as the position of the coordinating atoms. The C-H activation of the Schiff bases was most facile in the formation of a Ru-CNO configuration followed by Ru-CNS, Ru-CNN, and Ru-CNC configurations, whereas for a Ru-NC(methine) configuration the activation was the slowest. X-ray crystal structures for five cycloruthenated complexes are reported. Detailed electrochemical studies reveals the redox behavior of the complexes and DFT calculations were performed to obtain geometry optimized structure of all other complexes and to get an insight of the electronic spectral behavior.

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

9/18/21 News Some scientific research about Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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A new crystalline polymorph of known chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium(II) complex [RuCl(PPh3)2(eta5-C5H5)] was obtained and characterized by various analytical methods including single-crystal and powder X-ray diffraction (XRPD) and differential scanning calorimetry (DSC) in combination with thermo-gravimetric analysis (TG-DSC). The obtained crystals of new polymorph are monoclinic, space group P21/n, with a = 11.125(4), b = 19.184(6), c = 15.946(5) A, alpha = 90, beta = 100.174(5), gamma = 90, and Z = 4. It has been found that real melting point of the complex (M.p. = 252-253 C) can be determined only in inert atmosphere while an apparent melting is observed in the range 142-150 C due oxygen promoted oxidative dissociation of triphenylphosphine ligand.

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

09/17/21 News Can You Really Do Chemisty Experiments About Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data.COA of Formula: C41H35ClP2Ru, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 32993-05-8, in my other articles.

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Four new cyclopentadienylruthenium(II)-acetophenone-4(N)-substituted thiosemi-carbazone complexes, with the general formula [Ru(?5-C5H5)(H-Aptsc)PPh3].Cl (1), [Ru(?5-C5H5)(H-Apmtsc)PPh3].Cl (2), [Ru(?5-C5H5)(H-Ap-etsc)PPh3].Cl (3) and [Ru(?5-C5H5)(H-Ap-ptsc)PPh3].Cl (4) were synthesised and characterised (1H NMR, 13C NMR, IR and electronic spectroscopy). The molecular structure of representative complexes 2 and 3 was confirmed by single crystal X-Ray diffraction technique. The binding ability of complexes (1?4) to calf-thymus DNA (CT DNA) and Bovine Serum Albumin (BSA) has been explored by absorption and emission titration methods. Based on the observations, an electrostatic and an intercalative binding mode have been proposed for the complexes with CT-DNA. The BSA protein binding studies have been monitored by quenching of tryptophan and tyrosine residues in the presence of complexes and static type of quenching mechanism has been proposed. In vitro free radical scavenging activity was performed by DPPH radical. The complexes (1?4) exhibited highest scavenging activity than conventional standard vitamin C (IC50 = 5.65 ± 0.12). Further, antibacterial activity of the complexes has been screened against four pathogenic bacteria such as Salmonella paratyphi, Staphylococcus aureus, Escherichia coli and Bacillus subtilis. From the results it is found that all the complexes exhibited significant activity against the pathogens and among them, complex 3 exhibited higher activity.

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

9/17 News Can You Really Do Chemisty Experiments About Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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The synthesis of polyaryl phosphonium salts by cyclotrimerization of aryl alkynes is induced by a stoichiometric amount of the ruthenium eta5-pentadienyl complex (eta5-C5H7)(PPh3)2RuCl (1). With only 1 mol % quantity, complex 1 efficiently catalyzed the dimerization of aryl alkynes at room temperature to afford the corresponding (Z)-1,4-diarylbut-1-en-3-yne derivatives as the major products.

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

9/16 News Can You Really Do Chemisty Experiments About Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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The vinylidene complex [Ru(eta5-C5H 5)(PPh3)2(CCHUr)][X] (X = PF6, OTf, Ur = uracil) is a versatile precursor for a range of organometallic complexes containing pendant uracil groups. Using appropriate conditions the vinylidene complex may be selectively transformed into alkynyl Ru(-CCUr)(eta5- C5H5)(PPh3)2, carbene [Ru(eta5-C5H5)(PPh3) 2(C{OMe}-CH2Ur)][X] and alkenyl-phosphonio species [Ru(E-CHC{PPh3}Ur)(eta5-C5H 5)(PPh3)2][X]. The synthesis of the related alkenyl-phosphonio complexes [Ru(E-CHC{PPh3}R)(eta5- C5H5)(PPh3)2][X] (R = Ph, C 6H4-3-OMe) is described; these undergo a further orthometallation reaction: the mechanism of this latter reaction appears to proceed via dissociation of a ruthenium-bound PPh3 ligand. The Royal Society of Chemistry 2009.

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

9/16/21 News Awesome and Easy Science Experiments about Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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Ruthenium sigma-acetylides with an end-capping organic electron acceptor and thienyl entity in the conjugation chain, Ru(C?C – Y)(PPh3)2(eta5-C5H5) (Y = th-CHO, th-CH=C(CN)2, th-(E)-CH=CH-th-CHO, th-(E)-CH=CH-th-CH=C(CN)2, C6H4-(E)-CH=CH-th-NO2, th-(E)-CH=CHC6H4-4-NO2, C6H4C?C-th-NO2, th-(E)-CH=CH-th-CH=CHC6H4-4-NO2, C6H4N=C(H)-th-NO2, th-(E)-CH=CHC5H4N+Me, th-C?CC5H4N+Me, th-(E)-CH=CH-th-NO2, th-C?C-th-NO2) (th = 2,5-disubstituted thiophene), were synthesized. These complexes exhibit intense charge transfer from the ruthenium donor to the organic acceptor. The quadratic hyperpolarizabilities of the selected complexes were determined using the hyper Rayleigh scattering method Single-crystal X-ray analysis was employed to examine the structures of Ru-(C?CC6H4-(E)-CH=CH-th-NO2)(PPh 3)2(eta5-C5H5) and Ru(C?C-th-CH=C(CN)2)(PPh3)2(eta 5-C5H5).

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

15-Sep News Top Picks: new discover of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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Reaction of monophosphinite ligand, 2-(diphenylphosphinoxy)naphthyl, C 10H7OPPh2 (1) with elemental sulphur or selenium gives the corresponding sulphide C10H7OP(S) Ph2 (2) or selenide C10H7OP(Se)Ph2 (3) derivatives. Reaction of 1 with [CpRu(PPh3)2Cl] gives monosubstituted complex, [CpRu(C10H7OPPh 2)(PPh3)(Cl] (4) as well as the disubstituted complex, [CpRu(C10H7OPPh2)2Cl] (5) depending upon the reaction conditions. Treatment of 1 with [Rh(CO)2Cl] 2 affords a trans-complex, [Rh(CO)(C10H 7OPPh2)2Cl] (6). Reaction of 1 with [Pd(COD)Cl2] results in the formation of an unexpected chloro-bridged dipalladium complex; [Pd(PPh2O)(PPh2OH)(mu-Cl)] 2 (7), whereas similar reaction with [Pt(COD)Cl2] gives cis-[Pt(C10H7OPPh2)2Cl2] (8) in good yield.

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

15-Sep News Awesome and Easy Science Experiments about Chloro(pentamethylcyclopentadienyl)bis(triphenylphosphine)ruthenium(II)

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Copper catalyzed [3+2] cycloaddition reactions between ethynylferrocene and benzylazides yields 1-benzyl-4-ferrocenyl-1,2,3-triazoles (2-5). Reaction between phenylacetylene and azidoferrocene yields 1-ferrocenyl-4-phenyl-1,2,3-triazole (6). Anodic electrochemistry of 2-6 suggests reversible oxidation at potentials more positive than ferrocene. Chemical oxidation of 2 and 3-ferrocenylpyrrole (1) with dichlorodicyanoquinone (DDQ) yields the salts [2+{radical dot}] [DDQ{radical dot}-] and [1+{radical dot}] [DDQ{radical dot}-], respectively. 57Fe Moessbauer spectroscopy reveals the presence of low-spin FeII in [1+{radical dot}][DDQ{radical dot}-] while FeII is oxidized to low-spin FeIII in [2+{radical dot}][DDQ{radical dot}-]. Magnetization measurements indicate that [1+{radical dot}][DDQ{radical dot}-] is paramagnetic and cannot be viewed as a simple neutral charge transfer complex reminiscent of the mixed stack diamagnetic [ferrocene]0[TCNE]0.

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

14/9/2021 News Extended knowledge of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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The new ruthenium hydride complexes CpRuH(L) (L = PR2CH2CH2PR2, R = p-CF3C6H4 (dtfpe) or R = p-MeOC6H4 (dape)) were prepared by reaction of NaOMe with CpRuCl(L), which were obtained by treating CpRuCl(PPh3)2 with L. Similarly, Cp*RuH(L) (L = dppm, (PMePh2)2) were prepared from the reaction of NaOMe with Cp*RuCl(L) obtained from the reaction of Cp*RuCl2 with L in the presence of Zn. Protonation of CpRuH(L) (L = dtfpe, dape) and Cp*RuH(dppm) with HBF4-Et2O produces mixtures of [CpRu(H)2(L)]+ and [CpRu(eta-H2)(L)]+, and [Cp*Ru(H)2(dppm)]+ and [Cp*Ru-(eta2-H2)(dppm)]+. The pKa values of the dihydrogen/dihydride complexes [CpRuH2(L)]+ (L = dtfpe, dppm, dppe, (PPh3)2, dppp, dape) and [Cp*RuH2(L)]+ (L = dppm, (PMePh2)2) are determined by studying acid/base equilibria by 1H and 31P NMR spectroscopy in both CH2Cl2 and THF. The electrochemical properties of the monohydrido complexes CpRuH(L) and Cp*RuH(L) are reported. Peak potentials for oxidation of these monohydrides and pKa values of the cationic complexes are linearly related for all the complexes with a dihydrogen form: pKa(Ru(H2)+) = -10.7Epa(RuH+/RuH) + 13.0. As expected eta2-H2 acidity decreases as the parent hydride becomes easier to oxidize. The related complexes with just a dihydride form, [CpRu(H)2(L)]+ (L = (PPh3)2, dppp) and [Cp*Ru(H)2(PMePh2)2]+, give a similar trend. Acidity constants have been determined for both tautomers when they observed; the pKa of the eta2-H2 form is ?0.3 pKa unit less (more acidic) than that of the (H)2 form for the complexes with L = dtfpe, dppe, and dape but is 0.4 unit greater for [Cp*RuH2(dppm)]+. The acidities of the two tautomers are similar because their concentrations are similar and they have the same monohydrido conjugate base. Other trends in pKa, 1J(HD), and deltaRu(H2) values of dihydrogen complexes and ratio of dihydride to dihydrogen tautomers and the peak potentials for oxidation of the monohydrido complexes are presented. These correlations are shown to be of value in explaining/predicting the propensity of dihydrogen to undergo heterolytic cleavage. Extremes in pKa values of such cyclopentadienylruthenium(Il) complexes are expected for [Cp*RuH2(dmpe)]+ (pKa ? 12) and [CpRuH2(CO)2]+ (pKa ? -6).

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

14/9/2021 News Archives for Chemistry Experiments of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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The reactions of PTA (1,3,5-triaza 7-phosphaadamantane) and HMTA (1,3,5,7-tetraazaadamantane) with 1,3-propanesultone or 1,4-butanesultone gave the water soluble zwitterionic derivatives PTA+C3H 6SO3- (1), PTA+C4H 8SO3- (2), HMTA+C3H 6SO3- (3) and HMTA+C 4H8SO3- (4). The crystal structure of HMTA+C3H6SO3 is reported. The coordinative ability of 1-4 towards Pt(II) and Ru(II) has been investigated and the antiproliferative activity of ligands and complexes has been tested in two human ovarian cancer cell lines, A2780 and SKOV3.

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