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The synthesis of four novel heteroleptic dipyrrinato complexes [(eta6-arene)RuCl(2-pcdpm)] (eta6-arene = C 6H6, 1; C10H14, 2) and [(eta5-C5Me5)MCl(2-pcdpm)] (M = Rh, 3; Ir, 4) containing a new chelating ligand 4-(2-methoxypyridyl)-phenyldipyrromethene (2-pcdpm) have been described. The complexes 1-4 have been fully characterized by various physicochemical techniques, namely, elemental analyses, spectral (ESI-MS, IR, 1H, 13C NMR, UV/vis) and electrochemical studies (cyclic voltammetry (CV) and differential pulse voltammetry (DPV)). Structures of 3 and 4 have been determined crystallographically. In vitro antiproliferative and cytotoxic activity of these complexes has been evaluated by trypan blue exclusion assay, cell morphology, apoptosis, acridine orange/ethidium bromide (AO/EtBr) fluorescence staining, and DNA fragmentation assay in Dalton lymphoma (DL) cell lines. Interaction of 1-4 with calf thymus DNA (CT DNA) has also been supported by absorption titration and electrochemical studies. Our results suggest that in vitro antitumor activity of 1-4 lies in the order 2 > 1 > 4 > 3.

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

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In order to address outstanding questions about ruthenium complexes in complex biological solutions, 19F NMR spectroscopy was used to follow the binding preferences between fluorinated RuII(eta6-arene)(bipyridine) complexes and protected amino acids and glutathione. Reporting what ruthenium compounds bind to in complex environments has so far been restricted to relatively qualitative methods, such as mass spectrometry and X-ray spectroscopic methods; however, quantitative information on the species present in the solution phase cannot be inferred from these techniques. Furthermore, using 1H NMR, in water, to distinguish and monitor a number of different complex RuII(eta6-arene) adducts forming is challenging. Incorporating an NMR active heteroatom into ruthenium organometallic complexes provides a quantitative, diagnostic ‘fingerprint’ to track solution-phase behaviour and allow for unambiguous assignment of any given adduct. The resulting 19F NMR spectra show for the first time the varied, dynamic behaviour of organoruthenium compounds when exposed to simple biomolecules in complex mixtures. The rates of formation of the different observed species are dramatically influenced by the electronic properties at the metal, even in a closely related series of complexes in which only the electron-donating properties of the arene ligand are altered. Preference for cysteine binding is absolute: the first quantitative solution-phase evidence of such behaviour.

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

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The complexation with organoruthenium fragments confers 4-anilinoquinazoline pharmacophores with higher potential for inducing cellular apoptosis while the highly inhibitory activity of 4-anilinoquinazolines against EGFR and the reactivity of the ruthenium centre to 9-ethylguanine are well preserved.

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

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Compounds derived from the reactions of dimeric arene ruthenium [{(eta6-arene)Ru(mu-Cl)Cl}2] (arene = benzene and p-cymene) and structurally analogous rhodium and iridium complexes [{(eta5-C5Me5)M(mu-Cl)Cl}2] (M = Rh or Ir) with 2-chloro-4,6-(di-2-pyridylamino)-1,3,5-triazine (cddt) and 2,4,6-tris(di-2-pyridylamino)-1,3,5-triazine (tdat) are reported. Compounds under investigation have been characterized by elemental analyses, NMR ( 1H and 13C), electronic absorption, emission spectral and electrochemical studies. Structures of the dinuclear compounds [{(eta6-C10H14)RuCl}2(cddt)] (PF6)2, [{(eta5-C5Me 5)RhCl}2(cddt)]Cl2·6H2O and trinuclear compound [{(eta6-C6H6)RuCl} 3(tdat)]Cl3·4H2O have been determined crystallographically. Among cddt containing compounds the {(eta6- C10H14)RuCl}- units in [{(eta6-C 10H14)RuCl}2(cddt)](PF6) 2 are anti, while {(eta5-C5Me 5)RhCl}- in the rhodium compound [{(eta5-C 5Me5)RhCl}2(cddt)]Cl2·6H 2O are syn with respect to triazine ring. Cyclic voltammetric studies on the compounds suggested lack of communication between the metal centres. Furthermore, although tdat is luminescent at room temperature compounds under investigation containing this ligand are non-luminescent in acetonitrile. Compounds derived from the reactions of dimeric arene ruthenium [{(eta6-arene)Ru(mu-Cl)Cl}2] (arene = benzene and p-cymene) and structurally analogous rhodium and iridium complexes [{(eta5-C5Me5)M(mu-Cl)Cl}2] (M = Rh or Ir) with 2-chloro-4,6-(di-2-pyridylamino)-1,3,5-triazine (cddt) and 2,4,6-tris(di-2-pyridylamino)-1,3,5-triazine (tdat) are described. Compounds under study have been fully characterized by analytical, spectral and electrochemical studies and structures of [{(eta6-C 10H14)RuCl}2(cddt)](PF6) 2, [{(eta5-C5Me5)RhCl} 2(cddt)]Cl2·6H2O, and [{(eta6-C6H6)RuCl}3(tdat)]Cl 3·4H2O have been authenticated crystallographically.

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

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We synthesize optically active (R)-terbutaline 2, which is an anti-asthmatic drug, through recyclable catalytic asymmetric transfer hydrogenation (RCATH). Various chloroketones 4 were prepared and RCATH was performed on them. The products exhibit moderate to high enantioselectivity. In particular, the hydrogenation of acyl substituted substrates 4c yields chiral secondary alcohols 5c in good yield and enantioselectivity. Furthermore, (R)-terbutaline 2 can be synthesized in one step from the resulting secondary alcohol 5 without racemization.

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

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Programmed assembly of two different ligands with metallic ions: Generation of self-supported Noyori-type catalysts for heterogeneous asymmetric hydrogenation of ketones

Programmed assembly strategy has been first applied to the generation of self-supported Noyori-type catalysts for asymmetric hydrogenation of ketones by spontaneous heterocoordination of bridged diphosphine and diamine ligands with Ru(II) metallic ions. The immobilized catalyst demonstrates excellent enantioselectivity and activity in the heterogeneous catalysis of the hydrogenation of aromatic ketones and can be recovered and recycled at least seven times without obvious loss of selectivity and activity. Copyright

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

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Complexes of Pd(II), 6-C6H6Ru(II), and 5-CpRh(III) with Chalcogenated Schiff Bases of Anthracene-9-carbaldehyde and Base-Free Catalytic Transfer Hydrogenation of Aldehydes/Ketones and N-Alkylation of Amines

The condensation of 2-(phenylsulfanyl)ethylamine and 2-(phenylselenyl)ethylamine with anthracene-9-carbaldehyde resulted in Schiff bases [PhS(CH2)2C-N-9-C14H9](L1) and [PhSe(CH2)2C-N-9-C14H9] (L2), respectively. Na2[PdCl4] treatment of L1/L2 in acetone-water mixture for 3 h at room temperature gave palladacycle [PdCl(C-, N, S/Se)] (1/2; L1/L2-H = (C-, N, S)/(C-, N, Se)). The reaction of [(6-C6H6)RuCl(mu-Cl)]2 with L1/L2 in methanol for 8 h at room temperature (followed by addition of NH4PF6) afforded half-sandwich complex [(6-C6H6)Ru(L)Cl][PF6], 3/4: (L = L1/L2 – (N, E) ligand). The reaction of [(5-Cp)RhCl(mu-Cl)]2 with L1 /L2 in the presence of CH3COONa at 50 C (followed by treatment with NH4PF6) resulted in [(5-Cp)Rh(L-H)][PF6], 5/6: (L = L1/L2). On carrying out the reaction of [(5-Cp)RhCl(mu-Cl)]2 with these ligands at room temperature and in the absence of CH3COONa, complex [(5-Cp)Rh(L)Cl][PF6], 7/8 (L = L1/L2 – (N, E) ligand), was formed. Complexes 1-8 were authenticated with 1H, 13C{1H}, and 77Se{1H} NMR spectroscopy, high-resolution mass spectrometry, elemental analyses, and single-crystal X-ray diffraction. The moisture- And air-insensitive complexes of Pd(II) (1, 2), Ru(II) (3, 4) and Rh(III) (5-8) were thermally stable. Palladium and rhodium (under base-free condition) species efficiently catalyzed transfer hydrogenation (propan-2-ol as H-source). At room temperature conversion was 90% in TH catalyzed with 0.2 mol % of 2. N-Alkylation of aniline with benzyl alcohol under base-free condition was promoted by 3-8. The 7 was most efficient for the two base-free catalytic reactions. For TH optimum loading of 1-2 and 5-8 as catalyst is 0.05-0.2 and 0.2-0.5 mol % respectively. The optimum temperatures are 80 and 100 C for TH and N-alkylation, respectively. The optimum loading of 3-8 for N-alkylation is 0.5 mol %. Mercury poisoning test supported homogeneous pathway for the two catalytic reactions. The rhodacycles probably gave real catalytic species by losing a Cp? group.

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

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Protic Ruthenium Tris(pyrazol-3-ylmethyl)amine Complexes Featuring a Hydrogen-Bonding Network in the Second Coordination Sphere

We synthesized ruthenium complexes bearing a tris(pyrazol-3-ylmethyl)amine ligand LH3 and revealed that this tripodal ligand allows predictable accumulation of three proton-delivering NH groups around a coordination site. The Bronsted acidity of the NH groups in LH3 led to the formation of multiple hydrogen bonds with the substrate ligand and deprotonation. The chlorido complex ligated by LH3 catalyzed disproportionation of 1,2-diphenylhydrazine.

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

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Comparative study on ortho-C-H vs ortho-C-X (X = C, Cl, S) bond activation in ortho-Caromatic-N bond fusion in substituted anilines using ruthenium(II) mediators: Isolation and characterization of unusual Ru 2 complexes

The chemical reactions of a selection of ortho-mono- and disubstituted anilines with two ruthenium polyene mediator complexes, CpRu IICl(PPh3)2 (Cp- = cyclopentadienyl anion) and (Bnz)2RuII2Cl4 (Bnz = benzene), have been undertaken with a primary aim to make a comparison between ortho-C-H and ortho-C-X (X = Cl, C, S) bond activation processes in ortho-C-N bond fusion reactions. The reaction of ortho-monosubstituted anilines, viz., 2-chloroaniline (HL1a), 2-methylaniline (HL1c), and 2-methylthioaniline (HL1b), with CpRuIICl(PPh 3)2 yielded mononuclear complexes [CpRuIIL 2a-cCl] (1, 3, and 5), containing in situ generated ligands N-(aryl)-ortho-quinonediimine, L2a-c, along with anilido-bridged RuIII2 complexes (2, [CpClRuIII{mu- eta2-(L1a)-}]2; 4, [CpClRu III{mu-eta2-(L1c)-}] 2; and [6]Cl2, [CpRuIII{mu-eta2: eta1-(L1b)-}]2), respectively. The new ligands, L2a-c are formed via ortho-C-H bond activation reactions, whereas ortho-C-X bonds remained unaffected. However, the ortho-C-Cl bond activation reaction is also noted in the reaction between CpRu IICl(PPh3)2 and ortho-disubstituted aniline 2,6-dichloroaniline (HL3a) in more forceful conditions. The ruthenium(III) binuclear complex [CpRuIII{mu-eta2: eta1-(L3a)-}(mu-eta2: eta1-L2d)(mu-eta2-acetate)Ru IIICl]Cl, [7]Cl, of an in situ generated N-(2,6-dichlorophenyl)-6- chloro-ortho-quinonediimine ligand, L2d, has been isolated from the above reaction. The ligand L2d coordinates in a eta2- binding mode through an imine (=NH) nitrogen atom. The coordination mode of 2,6-dichloroanilide, (L3a)-, in [7]Cl is unusual in that an aromatic-C-Cl group is coordinated to a Ru(III) center, and it represents the first authentic crystallographic evidence of such a coordination mode in a transition metal complex. Similar reactions on a redox-inert mediator complex, (Bnz)2RuII2Cl4 (Bnz = benzene), with the aforesaid aromatic amines failed to result in ortho-C-N bond fusion reactions and afforded the mononuclear anilino complexes and an anilido-bridged RuII2 compound, [9]Cl2. The complexes have been characterized by using a host of physical methods as well as single-crystal X-ray structure determination. Their redox and spectroscopic properties have been thoroughly characterized by cyclic voltammetry and UV-vis and electron paramagnetic resonance spectroscopy. Density-functional theory calculations were employed to confirm their structural features and to support the spectral and redox properties.

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

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The reaction of [(eta6-C6H6)RuCl(mu-Cl)]2 with chalcogenoether substituted 1H-pyrazole ligands (L1-L3) in methanol have yielded three novel Ru(II) half-sandwich complexes [(eta6-C6H6)RuCl(L)]PF6 (1?3) in high yield under the ambient reaction conditions. The NMR, MS and FT-IR analytical techniques were used to identify their structures. The molecular structures of the complexes 2 and 3 were established with X-ray crystallographic analysis and revealed a pseudo-octahedral half sandwich piano-stool geometry around ruthenium in each complex. Complexes 1?3 are thermally robust and were found to be insensitive towards the air and moisture. All the complexes were found to be catalytically active and produced the excellent yields of amides (up to 95%) from corresponding aldehydes. In contrast to the previous reported catalytic systems for aldehyde to amide transformation, the present complexes 1?3 are very efficient and have several advantages in terms of low catalyst loading, reaction time, temperature and wide applicability for various substituted aldehydes. Owing to the stronger sigma-donor coordination properties of selenium containing ligands, the complex 2 was found to be more efficient as compare to the sulphur and tellurium analogues.

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