Synthesis and characterisation of [RuCl2(PPh3)2(C16H11NO)] complex

The reaction of [RuCl₂(PPh₃)₃] complex with 1-isoquinolyl phenyl ketone has been examined. A new ruthenium(II) complexes–[RuCl₂(PPh₃)₂(C₁₆H₁₁NO)] has been obtained and characterised by IR and UV-VIS measurements. Crystal structure of the complex has been determined. The electronic spectrum of the complex has been calculated by TDDFT method.     

trans-[RuCl2(phosphane)2(1,2-diamine)] and Chiral trans-[RuCl2(diphosphane)(1,2-diamine)]: Shelf-Stable Precatalysts for the Rapid,Productive, and Stereoselective Hydrogenation of Ketones

A turnover number (TON) of 2 400 000 and a turnover frequency (TOF) of 63 s⁻¹ are achieved with the chiral Ru^II complex 1 (R=p-CH₃C₆H₄) in the asymmetric hydrogenation of acetophenone. Carbonyl-selective asymmetric hydrogenation of α,β-unsaturated ketones proceeds in the presence of these Ru^II catalysts, and 4-substituted cyclohexanones are selectively converted into cis alcohols.     

Synthesis and spectral studies of [RuCl(CO)(L)(PPh3)(B)] (HL = 2'-hydroxychalcones and B = PPh3, pyridine or piperidine) and their catalytic and biological applications

The reactions of [RuHCl(CO)(PPh3)2(B)] (B = PPh3, pyridine or piperidine) and 2'-hydroxychalcones led to the formation of [RuCl(CO)(PPh3)(L)(B)] (L = chalconate). The new complexes have been characterized by analytical and spectral (IR, electronic, 1H NMR and 31P NMR) data. They have been assigned an octahedral structure. The complexes have been used as catalysts for the aerial oxidation of cinnamyl alcohol. Some of the complexes have been tested in vitro for growth inhibitory activity against the bacteria E. coli, S. typhi and Pseudomonas sp. and the fungi A. fumigatus.     

Synthesis,crystal and spectroscopic characterization of [RuHCl(CO)(PPh3)2(pyrazine)]

The reaction of [RuHCl(CO)(PPh₃)₃] with pyrazine has been examined and a ruthenium(II) complex – [RuHCl(CO)(PPh₃)₂(C₄H₄N₂)] -- has been obtained. The compound has been studied by IR, UV–Vis spectroscopy, and X-ray crystallography. The molecular orbital diagram of the complex has been calculated with density functional theory (DFT). The spin-allowed singlet--singlet electronic transitions of the complex have been calculated with the time-dependent DFT method, and the UV–Vis spectrum of the compound has been discussed on this basis.     

Synthesis,spectroscopy and structure of cis,cis,trans:N,N;P,P;S,S-[bis(triphenylphosphine)] [bis(pyrimidine-2-thiolato)]ruthenium(II)

Reaction of RuCl₂(PPh₃)₃with pyrimidine-2-thione (HpymS) in a 1:2?mol ratio in dry benzene in the presence of triethylamine as base yielded a complex of stoichiometry [Ru(pymS)₂(PPh₃)₂] (1). This has been characterized using analytical data and IR, ¹H, ¹³C and ³¹P NMR spectroscopy. ¹H NMR confirmed the deprotonation of HpymS. ³¹P NMR spectra showed a single peak confirming equivalent P atoms. Complex 1 crystallizes in space group Pī and HpymS acts as a η²-N,S-deprotonated bidentate anionic ligand. The coordination geometry around the Ru center is distorted octahedral with cis dispositions of P atoms, as well as two N atoms of pymS^– and trans S atoms of pymS^–. Important bond distances and angles are: Ru–N, 2.119(2), 2.106(2); Ru–S, 2.4256(8), 2.4413(8); and Ru–P, 2.3266(7), 2.3167(7)?Å; P(2)–Ru(1)–P(1), 96.07(3); N(21)–Ru(1)–N(11), 83.46(9); and S(1)–Ru(1)–S(2), 153.02(3)°.     

Synthesis and crystal structure of nitrosoruthenium aquadiammine complex, [Ru(NO)(NH3)2Cl2(H2O)]Cl·H2O

The reaction between [RuNO(NH₃)₂(NO₂)₂OH] and an excess of 3 M HCl leads to denitration of the starting complex and precipitation of [Ru(NO)(NH₃)₂Cl₃]. Crystals of the tittle complex have been obtained by evaporation of the mother liquor at ambient temperature. The crystal structure of the product has been determined. The linear nitroso group and a water molecule are coordinated in the trans positions, three nitrogen atoms from NO and NH₃ ligands occupy the coordination octahedron face.     

钌配合物[Ru(bpy)2(PNT)]2+的合成、表征及与DNA相互作用研究

以cis-Ru(bpy)2Cl2·2H2O与PNT为原料合成钌(Ⅱ)多吡啶配合物[Ru(bpy)2(PNT)]2+(bpy=2,2’-联吡啶, PNT=2-[4’-(5-四唑基)苯基]咪唑-[4,5-f][1,10]邻菲咯啉), 通过元素分析、质谱和核磁共振波谱对该化合物进行了结构表征. 利用紫外-可见吸收光谱、荧光光谱、热变性和黏度实验研究了配合物与CT-DNA的相互作用, 实验结果表明, 该配合物以部分插入模式与DNA结合.     

Synthesis,characterization, DNA-binding and DNA-photocleavage studies of [Ru(bpy)2(pmip)] and [Ru(phen)2(pmip)] (pmip = 2-(2′-pyrimidyl)imidazo[4,5-f][1,10]phenanthroline

Two new Ru(II) complexes, [Ru(bpy)₂(pmip)]²⁺ (1) and [Ru(phen)₂(pmip)]²⁺ (2), have been synthesized and characterized by elemental analysis, ESI-MS and ¹H NMR spectra. Their DNA-binding properties were studied by means of UV–VIS, emission and CD spectra, thermal denaturation and viscosity measurements as well as their DNA-photocleavage properties. The experimental results show that both 1 and 2 can bind to DNA in an intercalative mode; the DNA-binding affinity of 2 is greater than that of 1, which suggests that the ancillary ligands have a significant effect on the spectroscopic properties and DNA-binding behavior of the Ru(II) complexes. Under irradiation with UV light, the Ru(II) complexes show excellent efficiency of cleaving DNA. This research may provide valuable insight into the interactions of metal complexes with DNA, knowledge that is an excellent backdrop for the rational design of promising drugs.     

[Ru(phen)2dppz]2+二聚及对DNA键合性质的影响

研究发现, [Ru(phen)2dppz]2+表现出非常强的自聚合倾向, 并显著影响DNA的键合性质, 有关方面的研究应引起科研工作者的足够重视.     

Solvolysis Products of the Types [RhMeL2(Me3[9]aneN3)]2+ and [RuCl3—XLX(Me3[9]aneN3)](x)+ (x = 1‐2) and Preparation and Structure of [Ru([9]aneS3)(Me3[9]aneN3)](CF3SO3)2

Solvolysis of [RhMe(CF₃SO₃)₂(Me₃[9]aneN₃)] ( 1 ) (Me₃[9]aneN₃ = 1, 4, 7‐trimethyl‐1, 4, 7‐triazacyclononane) in CH₃CN, DMSO or pyrazole (L) leads to substitution of both trifluoromethylsulfonate ligands and formation of the cationic complexes [RhMeL₂(Me₃[9]aneN₃)](CF₃SO₃)₂ 3—5 . In contrast, treatment of [RuCl₃(Me₃[9]aneN₃)] ( 2 ) with Ag(CF₃SO₃) in a 1:3 ratio for 2h in CH₃CN leads to formation of the tetranuclear complex [{RuCl₃(Me₃[9]aneN₃)}₂Ag₂(CF₃SO₃)(CH₃CN)](CF₃SO₃) · CH₃CN ( 6 ) with a novel [(RuCl₃)₂Ag₂] core. More forcing conditions enable the substitution of respectively one or two chloride ligands by CH₃CN (reflux 18h) or DMF (85°C, 1h) to afford [RuCl₂(CH₃CN)(Me₃[9]aneN₃)](CF₃SO₃) ( 7 ) and [RuCl(DMF)₂(Me₃[9]aneN₃)](CF₃SO₃)₂ ( 8 ). The heteroleptic sandwich complex [Ru([9]aneS₃)(Me₃[9]aneN₃)](CF₃SO₃)₂ ( 9 ) can be prepared by reduction of 2 with Zn powder in acetone in the presence of 3 equiv. of Ag(CF₃SO₃), followed by addition of [9]aneS₃ (1, 4, 7‐trithiacyclononane). The redox potential E°(Ru³⁺/Ru²⁺) of +1.87 V vs NHE for 9 is only —0.12 V lower than that of the homoleptic complex [Ru([9]aneS₃)₂]²⁺. Crystal structures are reported for 3 — 9 .     

Synthesis,characterization, DNA-binding and DNA-photocleavage studies of [Ru(bpy)2(BPIP)] and [Ru(phen)2(BPIP)] (BPIP = 2-(4′-biphenyl)imidazo[4,5-f][1,10]phenanthroline)

New ligand 2-(4′-biphenyl)imidazo[4,5-f][1,10]phenanthroline (BPIP) and its complexes [Ru(bpy)₂(BPIP)]²⁺ (1) (bpy = 2,2′-bipyridine) and [Ru(phen)₂(BPIP)]²⁺ (2) (phen = 1,10-phenanthroline) have been synthesized and characterized by mass spectroscopy, ¹H NMR and cyclic voltammetry. The interaction of two Ru(II) complexes with calf thymus DNA (CT-DNA) was investigated by spectroscopic and viscosity measurements. Results indicate that both complexes bind to DNA via an intercalative mode and the DNA-binding affinity of complex 2 is much greater than that of complex 1. Furthermore, when irradiated at 365 nm, both complexes have also been found to promote the photocleavage of plasmid pBR 322 DNA.     

Synthesis and spectroscopic characterization of trinuclear [Ru3O(O2CCH3)6(pyrazine)3]0, + clusters

Summary [Ru₃O(O₂CCH₃)₆(pyrazine)₃]^{0, +} clusters have been synthesized and characterized based on electronic, infrared and resonance Raman spectra. Selective enhancement of the pyrazine and Ru₃O(O₂CCH₃)₆ vibrational modes has been observed in the case of the reduced cluster using excitation wavelengths close to the metal-to-pyrazine and metal-metal charge transfer band in the visible region.

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Synthese und spektroskopische Charakterisierung von dreikernigen [Ru₃O(O₂CCH₃)₆(Pyrazin)₃]^{0, +}-Clustern

Zusammenfassung Es wurden [Ru₃O(O₂CCH₃)₆(Pyrazin)₃]^{0, +}-Cluster dargestellt und mittels Elektronen-, Infrarot- und Resonanz-Raman-Spektren charakterisiert. Im Fall der reduzierten Cluster wurde bei Anregungswellenlängen nahe den Metall-Pyrazin- und Metall-Metall-Charge-Transfer-Banden im sichtbaren Bereich eine selektive Anhebung der Pyrazin- und Ru₃O(O₂CCH₃)₆-Vibrationen beobachtet.

     

Synthesis,characterization, and DNA-binding of [Co(phen)2(CPIA)]3+, [Co(phen)2(BIP)]3+, and [Co(phen)2(CIP)]3+

Three ligands, 2-(3-(carboxymethyl)-1,10-phenanthroline-[5,6-d]imidazole-1-yl)acetate (CPIA), 2-(benzo[d][1,3]dioxol-4-yl)-1H-imidazo[4,5-f][1,10]phenanthroline (BIP), and 2-(9H-carbazol-3-yl)-1H-imidazo[4,5-f][1,10]phenanthroline (CIP), and their complexes, [Co(phen)₂(CPIA)]³⁺ (1) (phen = 1,10-phenanthroline), [Co(phen)₂(BIP)]³⁺ (2), and [Co(phen)₂(CIP)]³⁺ (3), have been synthesized and characterized. Binding of the three complexes with calf thymus DNA (CT-DNA) has been investigated by spectroscopic methods, cyclic voltammetry, and viscosity measurements. The three complexes bind to DNA through an intercalative mode, and the size and shape of the intercalative ligands have significant effects on the binding affinity of complexes to CT-DNA.     

[RuCl3ind3] and [RuCl2ind4]: Two New Ruthenium Complexes derived from the Tumor‐inhibiting RuIII Compound HInd (OC‐6‐11)‐[RuCl4ind2] (ind = indazole)

Indazolium (OC‐6‐11)‐tetrachlorobis(indazole) ruthenate(III), HInd (OC‐6‐11)‐[RuCl₄ind₂], exhibits excellent results in different tumor models in vitro and in vivo. Substitution reactions of this ruthenium(III) complex are of special interest for a deeper understanding of its interactions with biologically occurring targets and its mode of action. The indazolium complex salt can be transformed to the neutral, meridionally configurated trisindazole complex (OC‐6‐21)‐[RuCl₃ind₃] in solvents like tetrahydrofuran. The X‐ray crystal structure of this complex could be solved (monoclinic space group P2(1)/n, a = 12.441(3), b = 10.415(3), c = 21.635(4) Å, β = 105.02(1)°). In spite of the paramagnetic Ru^III atom most of the coordinated indazole protons could be assigned with the help of two‐dimensional NMR experiments. Additionally, a reduced reaction product of HInd (OC‐6‐11)‐[RuCl₄ind₂] in the physiological solubilizer 2‐pyrrolidone could be isolated and the X‐ray crystal structure of this Ru^II complex, (OC‐6‐12)‐[RuCl₂ind₄], crystallized with two 2‐pyrrolidones, could be solved (monoclinic space group P2(1)/n, a = 12.139(2), b = 10.426(2), c = 14.426(3) Å, β = 100.06(3)°).     

[RuCl2{PPh2(2,6-Me2C6H3)}2]: A Neutral 14-Electron Ruthenium(II) Complex with Two Agostic Interactions

“Bidentate” ligand behavior is shown by (2,6-dimethylphenyl)diphenylphosphane in the title compound: In the nearly octahedral environment of the ruthenium atom two coordination sites are occupied by methyl groups of the two xylyl substituents. NMR investigation and an X-ray analysis (see picture) reveal that the methyl groups act as weak donors to form two strong agostic Ru⋅⋅⋅C−H interactions.     

meso-四(4-磺基苯基)卟啉(TPPS)在水及胶束体系中的二聚行为研究

研究了meso-四（4-磺基苯基）卟啉（TPPS）在胶束（TritonX－100）、KCl水溶液中的电子吸收光谱变化,计算了TPPS的二聚常数KD,用分光光度法研究了TPPS在KCI水溶液中的二聚反应动力学,提出了与实验结果相吻合的二聚机理．根据温度对二聚平衡的影响,计算了二聚平衡的乙和     

Effect of the ancillary ligands on the binding of ruthenium(II) complexes [Ru(dmp)2(MCMIP)]2+ and [Ru(dmb)2(MCMIP)]2+ with DNA

Two polypyridine ruthenium(II) complexes, [Ru(dmp)₂(MCMIP)]²⁺ (1) (MCMIP = 2-(6-methyl-3-chromonyl)imidazo[4,5-f][1,10]-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline) and [Ru(dmb)₂(MCMIP)]²⁺ (2) (dmb = 4,4′-dimethyl-2,2′-bipyridine), have been synthesized and characterized by elemental analysis, ES-MS and ¹H NMR. The DNA-binding behaviors of these complexes were investigated by electronic absorption titration, fluorescence spectroscopy, viscosity measurements and thermal denaturation. The results show that 1 and 2 effectively bind to CT-DNA; the DNA-binding affinities are closely related to the ancillary ligand.