Synthesis, DNA-binding and photocleavage studies of ruthenium(Ⅱ) complexes [Ru(btz)_3]~(2+) and [Ru(btz)(dppz)_2]~(2+)

Two new ruthenium(Ⅱ) complexes, [Ru(btz)3](ClO4)2 (1) and [Ru(btz)(dppz)2](ClO4)2 (2) (btz = 4,4′-bithi-azole, dppz = dipyrido[3,2-a:2′,3′-c]phenazine), have been synthesized and characterized by elemental analysis, 1H NMR, ES-MS and X-ray crystallography. The DNA binding behaviors of two complexes have been studied by spectroscopic and viscosity measurements. The results suggest that complex 1 binds to CT-DNA via an electrostatic mode, while complex 2 via an intercalative mode. Under irradiation at 365 nm,...     

Redox-switchable binding of the Mg2+ ions by 21,31-diphenyl-12,42-dioxo-7,10,13-trioxa-1,4(3,1)-diquinoxaline-2(2,3),3(3,2)-diindolysine-cyclopentadecaphane

The binding of the Li⁺, Na⁺, K⁺, Mg²⁺, and Co²⁺ ions by 2¹,3¹-diphenyl-1²,4²-dioxo-7,10,13-trioxa-1,4(3,1)-diquinoxaline-2(2,3),3(3,2)-diindolysine-cyclopentadecaphane containing two indolysine fragments, two quinoxaline fragments, and 3,6,9-trioxyundecane spacer in the acetonitrile/0.1 M Bu₄NBF₄ environment is studied by the method of cyclic voltammetry. It is demonstrated that the Li⁺, Na⁺, K⁺, and Co²⁺ ions are not bound by this macrocycle, whereas selective redox-switchable binding is observed for the Mg²⁺ ions. The macrocycle binds the Mg²⁺ ions way more efficiently as compared with its radical cation and dication. The indolysinequinoxaline fragments play the determining role in the binding. Original Russian Text ? V.V. Yanilkin, N.V. Nastapova, V.A. Mamedov, A.A. Kalinin, V.P. Gubskaya, 2007, published in Elektrokhimiya, 2007, Vol. 43, No. 7, pp. 808–814.     

Synthesis of Li(x)Na(2−x)Mn2S3 and LiNaMnS2 through redox-induced ion exchange reactions

Na₂Mn₂S₃ was oxidatively deintercalated using iodine in acetonitrile to yield Na_1.3Mn₂S₃, with lattice constants nearly identical to that of the reactant. Lithium was then reductively intercalated into the oxidized product to yield Li_0.7Na_1.3Mn₂S₃. When heated, this metastable compound decomposed to form a new crystalline compound, LiNaMnS₂, along with MnS and residual Na₂Mn₂S₃. Single crystal X-ray diffraction structural analysis of LiNaMnS₂ revealed that this compound crystallizes in P-3m1 with cell parameters a=4.0479(6) Å, c=6.7759(14) Å, V=96.15(3) Å³ (Z=1, wR2=0.0367) in the NaLiCdS₂ structure-type.     

Synthesis and Efficiency of Poly(Acryl- p-Nitrophenylamidrazone- p-Nitrophenylhydrazide) Chelating Fibre for Pre-Concentration and Separation of Trace Concentrations of Bi 3+, In 3+, Sn 4+, Ga 3+ and Ti 4+

A new poly(acryl-p-nitrophenylamidrazone-p-nitrophenylhydrazide) chelating fibre was synthesized from polyacrylnitrile fibre, and the structure of the chelating fibre was determined with the help of the FT-IR spectrum. The parameters influencing the efficiency of the fibre for concentrating trace amounts of Bi³⁺, In³⁺, Sn⁴⁺, Ga³⁺ and Ti⁴⁺, including sample acidity during enrichment, flow rate, adsorptive capacity, re-usability, interfering ions and desorption conditions were investigated. Trace Bi³⁺, In³⁺, Sn⁴⁺, Ga³⁺ and Ti⁴⁺ were enriched and separated from real sample solutions and detected using inductively coupled plasma optical emission spectrometry (ICP-OES) with satisfactory results. The experiments show that the method is rapid, precise, simple and convenient to use.     

A pios study of the reaction Ne(3P2,0) + HCl → Ne + HCl+ (A2Σ+) + e−

The HCl⁺ (A) vibrational state distributions from the title reaction were studied over the 48–110 meV collision energy range. The $\text{1}\text{0}$ and $\text{2}\text{0}$ ratios increase by factors of about 1.3 and 2.5, respectively. The branching ratios appear to be determined primarily by Franck-Condon factors, and by the endoergicity of the ν′ = 2 level.     

Proton transfers in hydrogen bonded systems. Electron correlation effects in (H3NHOH2)+

The energetics of proton transfer between the N and O atoms of (H₃NHOH₂)⁺ are calculated via ab initio molecular orbital methods. A single-well potential is obtained at the equilibrium intermolecular separation Inclusion of electron correlation via the POL CI technique produces a less steep potential, reducing the energy barrier to proton transfer at greater NO distances.     

An ab initio description of the excited states of the reaction O(3P, 1D) + H2 → OH(2Π, 2Σ+) + H. An attempt to describe several potential energy surfaces with constant accuracy

A new aspects of the role of the solvent mode in the photoinduced electron-transfer process of electron donor and acceptor system in polar solvents has been exploited. Taking into account the important fact that the vibrational frequency of the solvent mode in the initial neutral state of the reactants is considerably smaller than that in the final ionic state, we have derived a new formula for the energy-gap dependence of the electron-transfer rate. In this formulation, the activation energy is greatly reduced and the electron-transfer rate is almost independent of the energy gap over a wide down-hill energy region. This qualitative feature explains the experimental results for the relation between the bimolecular quenching rate constant k_w and the standard free-energy change ΔG° associated with electron transfer in the “anomalous region”.     

Magic cluster ion distributions: (NO)3+ (N2O)n and (NO)3+ (CO2)n

Supersonic jet expansions of mixtures of nitric oxide with either nitrous oxide or carbon dioxide have been investigated over a wide range of relative concentrations. Mixed molecular cluster ions of the form (NO) _m ⁺ (N₂O)_n and (NO) _m ⁺ (CO₂)_n are detected following non-resonant two-photon ionization. Over a wide range of intermediate concentrations, the cluster ion distributions (NO) ₃ ⁺ (N₂O)_n and (NO) ₃ ⁺ (CO₂)_n with n30 are significantly more intense than clusters containing other numbers of nitric oxide molecules. The extra abundance of these species is attributed to their especially stable structures and several possible forms are discussed. An intriguing possibility involves a stable cyclic nitric oxide trimer (or ion) when combined with nitrous oxide or carbon dioxide clusters.     

Reductive elimination reaction of rhenium complexes trans-(η-C5Me5)Re(CO)2(chloroaryl)Cl

Thermal reaction of the chloroaryl-chloride complexes trans-(η⁵-C₅Me₅)Re(CO)₂(Ar^Cl)Cl (Ar^Cl = 3-ClC₆H₄, 3-ClC₆H₃(4-Me) and 3,5-Cl₂C₆H₃) in acetonitrile did not interconvert to the cis isomer, instead the complex ReCl(CO)₂(NCMe)₃ and the corresponding 5-Ar^Cl-1,2,3,4,5-pentamethylcyclopentadiene were formed. Similar reductive elimination products were obtained when the starting rhenium complexes were reacted with trimethylphosphite in toluene.     

Synthesis and characterisation of some salts of the ions [Rh(Oxalato)2(Rpy)2]−

Salts of three bisoxalato bis(pyridine) species, trans-[Rh(ox)₂(py)₂]^?, trans-[Rh(ox)₂(3-Mepy)₂]^? and trans-[Rh(ox)₂(4-Mepy)₂]^? have been isolated from the substitution of N-heterocycles into trisoxalatorhodate(III) and characterised on the basis of ¹H NMR and ¹³C NMR spectra, which are similar to that of the trans-[Co(oxalato)₂ (R-py)₂]^? complex.     

Possible production of O2(1Δg) and O2(1Σ+g) in the reaction of NO with O3

High-resolution spectra of the NO₂ continuum emission produced from the reaction NO + O₃ → NO₂ + O₂ have been investigated to detect any possible emission from O₂(¹Δ_g) at 1270 nm or O₂(¹Σ⁺_g) at 762 nm. The photolysis of O₃/O₂ mixtures at 253.7 nm, which produces both states of O₂ with known quantum efficiency, has been used as an internal standard. From the results it is concluded that less than 1/300 and 1/200 of the NO + O₃ reactive collissions result in production of O₂(¹Δ_g) or O₂(¹Σ⁺_g), respectively, at room temperature.     

A crossed molecular beam study of the chemiluminescent reaction Xe(3P2,0) + BrCN → Xe(1S0) + Br + CN(B2Σ+)

The chemiluminescent interaction of Xe(³P_2,0) and BrCN has been studied under crosscd-beam conditions at collision energies ranging up to 70 kj mol^?1. The CN(B → X) fluorescence spectrum, the excitation function for its production and the fluorescence polarisation - or rather its absence - have been determined. The results can be explained by a two-stage harpooning mechanism involving an inert-gas cyanide (Xe⁺CN^?)¹ intermediate but not by a “sensitisation” mechanism proceeding through electronic energy transfer.     

12,52-二羟基-15,55-二甲基-14,16,34,36,54,56,74,76-八硝基-2,4,6,8-四氧桥连-1,3,5,7（1,3）-杯[4]芳烃的合成

以1,5-二氟-2,4-二硝基苯和3,4,5-三甲氧基甲苯为起始原料,经环化、甲基化、硝化和去甲基化反应,合成了一种新型杯芳烃衍生物,其结构经¹H NMR,¹³C NMR,¹⁵N NMR和元素分析表征。      

具有[344484]笼状结构单元的微孔磷酸镓Ga3P2O8(OH)3(H2O)的合成、晶体结构及表征

Open-framework metal phosphates have been the subject of intense research owing to their interesting structural chemistry and potential applications in catalysis and ion exchange. The gallium phosphate family has exhibits rich structural chemistry. A novel gallium phosphate Ga₃P₂O₈(OH)₃(H₂O)(GaPO-CJ36) has been prepared in a hydrothermal reaction system of GaO(OH)-H₃PO₄-Co(chxn)₃Cl₃-H₂O at 180 ℃ for 7 days. Single-crystal X-ray analysis shows that GaPO-CJ36 crystallizes in the P2₁/c space group with a=1.833 35(12) nm, b=0.503 94(3) nm, c=1.062 90(9) nm, V=0.982 01(12) nm³, and Z=4. The connection of GaO₂(OH)₃(H₂O) octahedra, PO₄ and GaO₄ tetrahedra through vertex oxygen atoms forms a three-dimensional open framework, which contains 8-ring channels along the [010] direction. Its structure is composed of interesting [3⁴4⁴8⁴] cages, which have not been found in known gallium phosphates. CSD: 416779.     

Density functional studies of influences of Ni triad metals and solvents on oxidative addition of MeI to [M(CH3)2(NH3)2] complexes and C-C reductive elimination from [M(CH3)3(NH3)2I] complexes

Three metal square planar complexes of the type [M(CH₃)₂(NH₃)₂] (M = Ni, Pd, Pt), with a systematic variation in the metals, are chosen to investigating their S_N2-type oxidative addition reactions with methyl iodide by using the B3LYP levels of theory. The oxidative addition was found to take place via a transition state with a nearly linear arrangement of the I-CH₃-M moiety. Solvation effects in these oxidative addition reactions were also investigated. Considering the nature of the metal centre and solvation effects, the following conclusions emerge: (i) addition of MeI is exothermic for all three metals, and Pt is predicted to react with a much lower barrier than either Pd or Ni. The results describe that the MeI addition would be expected to be more favourable with the complex bearing the third-row metal (platinum) as compared to the other triad metals, nickel or palladium, in which case a more strongly bound MeI adduct is formed with a lower activation barriers and the reaction being more exothermic; (ii) the reaction is very difficult to occur in low polar solvents, such as benzene, due to the high barrier which is induced by dissociation of iodide anion from methyl group, but the reaction easily occurs in polar solvents, such as acetonitrile; this is attributed to the ability of polar solvents to solvate and therefore stabilize the related polar intermediate ion pair. Ethane reductive elimination from the M(VI) complexes fac-[M(CH₃)₃(NH₃)₂I] were also studied, indicating that the Ni(IV) and Pd(IV) complexes are very prone to undergo the reductive elimination while the Pt(IV) analogous is less reactive towards the reductive elimination. The results indicate that in contrast to the Me-Me reductive elimination, the S_N2 oxidative addition reaction of MeI to M(II) is much less sensitive to the nature of the metal centre, suggesting that the nucleophilicity of M(II) in [M(CH₃)₂(NH₃)₂] does not change significantly as one moves from M = Ni to Pt.     

以[M(DETA)2)]n+(M=Cu2+, Ni2+, Co3+)为客体的MnPS3夹层化合物的合成、结构表征与磁性研究

将过渡金属配合物阳离子([M(DETA)₂]ⁿ⁺(M=Cu²⁺,Ni²⁺,Co³⁺;DETA=Diethylenetriamine,二乙烯三胺)作为客体插入层状MnPS₃层间得到了相应的3个夹层化合物。通过X-射线粉末衍射、元素分析和红外光谱对夹层化合物的结构进行了表征。结果表明,与主体MnPS₃ 0.65 nm的层间距相比较,夹层化合物(Mn_0.88PS₃[Cu(DETA)₂]_0.12)的层间距扩大了0.32 nm,由此推测客体[Cu(DETA)₂]²⁺在层间以平面四方的配位形式存在,而另2个夹层化合物(Mn_0.79PS₃[Ni(DETA)₂]_0.21和Mn_0.74PS₃[Co(DETA)₂]_0.17)的层间距扩大了0.48 nm,说明客体[(M(DETA)₂]ⁿ⁺,M=Co³⁺,Ni²⁺) 在主体层间以八面体配位形式存在。磁性测试结果表明过渡金属离子[(M(DETA)₂]ⁿ⁺(M=Cu²⁺,Co³⁺)的插入能引起主体MnPS₃的磁性在35~40 K发生由顺磁向亚铁磁性的转变并表现自发磁化,而客体[Ni(DETA)₂]²⁺却使夹层化合物的反铁磁相互作用增强,抑制了自发磁化的发生。     

Interactions of Eu3+(aq) 7F, 5D1 and 5D0 levels with nitrate and inner-sphere (EuNO2+3)* exciplex formation

Steady-state and transient photokinetic and spectroscopic measurements on aqueous Eu(NO₃)₃ show different affinities of ⁷F, ⁵D₁ and ⁵D₀ Eu³⁺_aq towards nitrate ion. This may be rationalised by differences in the inner- and outer-shell hydration structures between ⁵D_O, ⁵D₁ Eu³⁺(_aq) and ⁷F Eu³⁺_(aq). Nitrate penetration into the inner-shell of Eu³⁺_(aq), and inner-coordination (EuNO²⁺₃)^* exciplex formation, occur solely in the long-lived ⁵D_O level of Eu³⁺_(aq).     

Improved syntheses of Ru(CO)2 (O3SCF3)2 (bidentate) complexes and their conversion into new [Ru(CO)2 (bidentate)2]2+ complexes

Reaction of the complexes Ru(CO)₂Cl₂L [L = 2,2′-bipyridyl (bpy) or 1,10-phenanthroline (phen)] with trifluoromethanesulphonic acid under carefully controlled conditions yields Ru[cis-(CO)₂] [cis-(O₃SCF₃)₂] (bidentate complexes. From reactions of the trifluoromethanesulphonates with the appropriate bidentate ligands, the new complexes [cis-Ru(CO)₂-L(L′)]²⁺ (L as above; L′ = 4,4′-dimethyl-2,2′-bipyridyl or 4,4′-diisopropyl-2,2′-bipyridyl) as well as the known [_cis-Ru(CO)₂L₂]²⁺ and [cis-Ru(CO)₂bpy(phen)]²⁺ have been prepared.     

中位-四(对烷氧苯基 )卟啉 Co2+、Cu2+、Zn2+、Pb2+配合物的合成与表征

Synthesis of fourteen new complexes of meso-tetrakis(4-alkoxyphenyl) porphyrins with Co²⁺, Cu²⁺, Zn²⁺, Pb²⁺ were presented in this paper.Meso-tetrakis (4-alkoxyphenyl) porphyrins were prepared by condensation of 4-alkoxybenzaldehydes with pyrrole, then treated with corresponding metallic acetate to produce mentioned complexes, IR, UV, ¹H NMR, MS and elementary analysis were explored to confirm the structures of all theses new complexes.Characteristic spectrometric data of IR, UV, ¹H NMR related to these complexes have been systematically summarized.Ten of the fourteen complexes were found to exhibit liquid crystal properties.     

Thermal and photochemical production of chromate(VI) ions from some complexes containing the “CrNO”2+ group

Results are reported for the oxidation of complexes of the type [Cr(CN)_5?x(H₂O)_xNO]^x?3 by molecular oxygen in alkaline medium. In the case of the [Cr(CN)₅NO]^3? complex the reaction proceeded photochemically, whereas in othe cases the thermal oxidation was also observed. The influence of pH, CN^? concentration and energy of radiation was investigated.