Phanes with Three- and Four-Membered Rings as Building Elements

The systematic integration of the small 2π- and 4π-electron systems cyclopropenylium ion, cyclopropenone, oxo-cyclobutenylium ion, and cyclobutadiene into phane chemistry was initiated only a few years ago. [n₂]Cyclopropenylophanes, [n₂]cyclopropenonophanes, metal-capped [n₄]cyclobutadienosuperphanes, and other new families of double-decker phane species became available from cycloalkydiynes through special methods of double [2+1]cycloaddition with carbenes and metal complex induced dimerization by double [2+2]cycloaddition. Phane-specific structural features were elucidated by X-ray structural analyses. Cyclic voltammetry and PE spectroscopy as well as MO calculations reealed considerable interactions between closely spaced π-electron systems. Decapping cyclobutadienosuperphanes formally extended the synthetic principle to threefold [2+2]cycloadditions resulting in [n₄]-bridged tricyclo-[4.2.0.0^{3, 5}]octa-3,7-dienes, which represent a new type of cage compounds. Moreover, completion to fourfold [2+2]addition was achieved with the photoinduced transformation of [3₄]bridged tricyclo[4.2.0.0^{3, 5}]octa-3,7-diene into propella[3₄]cubane.     

Syntheses and Structures of Two New Cu/Nb/pyrazine Complexes: Three dimensional CuNb(pyz)2OF5 · (pyz)(H2O) and two dimensional [Cu(pyz)2.5]+ [NbF6]− · (pyz)

Crystals of CuNb(pyz)₂OF₅ · (pyz)(H₂O) ( 1 ) and [Cu(pyz)_2.5]⁺ [NbF₆]^? · (pyz) ( 2 ) were grown (150°C and autogeneous pressures) from CuO, 1/2(Nb₂O₅), (HF)_x · pyridine, and H₂O in excess pyrazine. Light blue single crystals of ( 1 ) are orthorhombic, crystallizing in space group Cccm (No. 66), with a = 14.547(1) Å, b = 16.135(2) Å, c = 13.803(2) Å, and Z = 8. The structure of ( 1 ) contains corner shared [Cu(pyz)_4/2F_2/2]⁺, [Cu(pyz)_4/2O_2/2], and [NbF₄O_1/2F_1/2]^?0.5 octahedra. Orange crystals of ( 2 ) are monoclinic, crystallizing in space group C2/c (No. 15), with a = 11.792(8) Å, b = 17.123(3) Å, c = 17.051(5) Å, β = 90.04(4)°, and Z = 8. The structure of ( 2 ) contains puckered rings of corner shared [Cu(pyz)(pyz)_3/2]⁺ tetrahedra and isolated [NbF₆]^? anions within the rings.     

Bis(diphenylphosphano)alkan- und 1-(Diphenylphosphano)-2-(2-pyridino)ethan-N-Arylsulfinylamin-Nickel(0)-Komplexe

Bis(diphenylphosphano)alkane- and 1-Diphenylphosphano-2-(2-pyridino)ethane-N-arylsulfinylamine Nickel(0) Complexes Synthesis and properties of the bis(diphenylphosphano)alkane-N-phenyl-sulfinylamine-nickel(0) complexes [Ni{Ph₂P(CH₂)_nPPh₂}(PhNSO)] (n = 2 dppe, n = 3 dppp, n = 4 dppb) as well as of the 1-(diphenylphosphano)-2-(2-pyridino)ethane nickel(0) complexes [Ni(dpppe)₂], [Ni(dpppe)(p-TolNSO)] and [Ni(dpppe)(PPh₃)₂] are described. These compounds have been characterized by i. r. and ³¹P n.m.r. spectroscopy. The N-arylsulfinylamine ligands are η²-(N, S)-side on coordinated.     

Zirconiumphthalocyanine: Darstellung und Eigenschaften chloridhaltiger Phthalocyanine des drei- und vierwertigen Zirconiums; Kristallstruktur von cis-Di(triphenylphosphin)iminium-tri(chloro)phthalocyaninato(2–)zirconat(IV)-di(dichlormethan)

Zirconiumphthalocyanines: Synthesis and Properties of Chloride Ligated Phthalocyanines of Ter- and Quadrivalent Zirconium; Crystal Structure of cis-Di(triphenylphosphine)iminium-tri(chloro)phthalocyaninato(2–)zirconate(IV)-di(dichloromethane) cis-Di(chloro)phthalocyaninato(2–)zirconium(IV) is obtained by the reaction of ZrCl₄ with phthalodinitrile in 1-chloronaphthaline at 230°C. It reacts with molten di(triphenylphosphine)iminiumchloride ((PNP)Cl) yielding cis-di(triphenylphosphine)iminium-tri(chloro)phthalocyaninato(2-)zirconate(IV), cis-(PNP)[ZrCl₃Pc^2?]. This crystallizes with two molecules of dichloromethane in the monoclinic space group P2₁/n with the lattice constants a = 15.219(4) Å, b = 20.262(10) Å, c = 20.719(4) Å, b? = 93.46(2)°, Z = 4. The seven coordinated Zr atom is situated in a “square base-trigonal cap” polyhedron. The plane of the three chlorine atoms runs parallel to the plane of the four isoindole nitrogen atoms N_iso. The Zr–Cl distances range from 2.49 to 2.55 Å, the Zr? N_iso distances from 2.26 to 2.29 Å. Due to ion packing effects the Pc^2? ligand shows an asymmetrical convex distortion. The PNP cation adopts the bent conformation. The P? N? P angle is 139°, the P? N distance 1.58 Å. As confirmed by the cyclovoltammograms cis-(PNP)[ZrCl₃Pc^2?] is oxidized (anodically or chemically by Cl₂) to yield cis-tri(chloro)phthalocyaninato(1–)zirconium(IV) and reduced (cathodically or chemically by [BH₄]^?) yielding chlorophthalocyaninato(2–)zirconium(III) and cis-di(triphenylphosphine)iminium-di(chloro)phthalocyaninato(2–)zirconate(III). The optical spectra show the typical π–π*-transitions of the Pc^2? resp. Pc^? ligand not much affected by the different states of oxidation and coordination of zirconium. The same is true for the vibrational spectra of the Pc^2? resp. Pc^? ligand. In the f.i.r. spectra between 350 and 150 cm^?1 the asym. and sym. Zr? Cl stretching and Cl? Zr? Cl deformation vibration as well as the asym. Zr? N stretching vibration of the [ZrCl_xN₄] skeleton (x = 1–3) is assigned.     

Synthesis and X-ray crystal structure of oxamido-bridged heterobinuclear Ni(Ⅱ)-Cu(Ⅱ) complexes

The two complexes [Ni(oxen)Cu(L)2](ClO4)2.xH2O (L=2,2'-bipyridyl(bpy), 1,10-phenanthroline(phen)) have been synthesized, where oxen is N,N'-bis(2-aminoethyl)oxamido di-anion. The crystal structure of [Ni(oxen)Cu(bpy)2](ClO4)2.CH3OH has been determined by X-ray diffraction method. The crystal is triclinic system, space group P1 with a=12.179(1),b=12.298(2), c=11.476(2) A, a=97.57(1), B=97.52(1), 7=80.29(2), V=1669.04(67) A3, Z=2, Dcalcd=1.667 g/cm3. The structure has been refined to final R of 0.076 and Rw of 0.080, respectively. The complexes have an extended oxamido-bridged structure and consist of Ni(Ⅱ) ion in a square planar environment and Cu(Ⅱ) ion in a distorted octahedral environment.     

A new platinum-osmium alkyne complex from the reaction of Pt2Os4(CO)18 with PhC ≡ CPh: The synthesis,characterization, and crystal structure of Pt2Os4(CO)8 (μ3-PhC2Ph)3(μ4-PhC2Ph)

The new platinum-osmium alkyne cluster complex Pt₂Os₄(CO)₈(₃-PhC₂Ph)₃ ( ₄-PhC₂Ph),2, was obtained from the reaction of Pt₂Os₄(CO)₁₈,1b, with PhC₂Ph and was characterized by IR.¹H NMR and single-crystal X-ray diffraction analyses. The cluster of compound2 consists of an osmium capped Pt₂Os₃ square pyramid. It aLso contains three triply bridging and one quadruply bridging diphenylacetylene ligands. Crystal data for2: space group PI,a = 12.530(2) Å,b = 21.565(4) Å,c = 11.284(2) Å, = 100.31(2), = 111.89(1), = 76.78(2),Z = 2, 3879 reflections,R = 0.032.     

Metal ion distribution and solubility of Mn1−xCux(HCOO)2 · 2 H2O Mixed Crystals [1–5]

The metal ion distribution on the two metal sites of monoclinic Mn_1?xCu_x(HCOO)₂ · 2(H,D)₂O mixed crystals are studied by infrared and Raman spectroscopic methods. The spectral regions 3 200–3 400 cm^?1 (v_OH), 2 875–2 990 cm^?1 (v_CH), 2 330–2 500 cm^?1 (v_OD of matrix isolated HDO molecules), 1 350–1 400 cm^?1 (symmetric CO₂ stretching modes), 570–950 cm^?1 (H₂O librations), and 490 cm^?1 (M? O lattice modes) are mostly sensitive to the metal ions present. The frequency shifts of these bands with increasing content of copper show that Cu²⁺ prefers the M(1) site, coordinated by HCOO^? only. The strengths of the hydrogen bonds increase on going from manganese to copper formate, due to the increased synergetic effect of Cu²⁺. Solubility and X-ray data of the mixed crystals are included. Irrespective of the same crystal structure, two series of mixed crystals are formed: eutonic area at 0.65 ≥ x ≥ 0.5.     

聚醚桥连二异羟肟酸单核和双核过渡金属配合物催化PNPP水解

Two polyether bridged dihydroxamic acids and their mono-and binuclear manganese(Ⅱ), zinc(Ⅱ) complexes have been synthesized and employed as models to mimic hydrolase in catalytic hydrolysis of p-nitrophenyl picolinate (PNPP). The reaction kinetics and the mechanism of hydrolysis of PNPP have been investigated. The kinetic mathematical model for PNPP cleaved by the complexes has been proposed. The effects of the different central metal ion, mono-and binuclear metal, the pseudo-macrocyclic polyether constructed by polyethoxy group of the complexes, and reactive temperature on the rate for catalytic hydrolysis of PNPP have been examined. The results showed that the transition metal dthydroxamates exhibited high catalytic activity to the hydrolysis of PNPP, the catalytic activity of binuclear complexes was higher than that of mononuclear ones, and the pseudo-macrocyclic polyether might synergetically activate H20 coordinated to metal ion with central metal ion together and promote the catalytic hydrolysis of PNPP.     

2,3-Dihydroxypyridine Loaded Amberlite XAD-2 (AXAD-2-DHP): Preparation, Sorption–Desorption Equilibria with Metal Ions, and Applications in Quantitative Metal Ion Enrichment from Water, Milk and Vitamin Samples

2,3-Dihydroxypyridine loaded (via –N=N–linker) Amberlite XAD-2 (AXAD-2-DHP) was prepared and characterized by elemental analyses, TGA and FT-IR spectra. It (1g packed in a column of 1cm diameter; surface area 135.5m²g^–1) was found to be an effective solid phase sorbent for enriching Zn²⁺, Mn²⁺, Ni²⁺, Pb²⁺, Cd²⁺, Cu²⁺, Fe³⁺ and Co²⁺ at pH 3.5 to 7.0 using flow rates between 1.0–5.0mLmin^–1. For desorption (recovery 97.0–99.8%) of the metal ions, 8 to 10mL of 2.0molL^–1 HCl or 1.5molL^–1 HNO₃ at a flow rate of between 2.0 and 4.0mLmin^–1 were found most suitable. The t_1/2 (time for 50% sorption) is between 2 and 10min when a 50mL solution (containing a total amount of metal of 2mg) was equilibrated with 0.5g of resin. Sorption of all metal ions except Pb²⁺ follows the Langmuir model, whereas for Pb the data fits with the Freundlich model. The sorption capacity is between 60.7 (for Cd) and 406.7 (for Cu) µmolg^–1. The resin can withstand an acid concentration of 6molL^–1 and can be reused for thirty cycles of sorption–desorption. The preconcentration factor varies between 100 and 300. For Cd, Ni and Cu the sorption capacity of 2,3-dihydroxypyridine loaded cellulose is lower than that of the present resin. The tolerance limits of electrolytes, humic acid, complexing agents, Ca²⁺ and Mg²⁺ in the enrichment of all metal ions are reported. The limits of detection are 3.88, 5.37, 8.72, 13.88, 4.71, 1.24, 0.59 and 0.30µgL^–1 for Zn²⁺, Mn²⁺, Ni²⁺, Pb²⁺, Cd²⁺, Cu²⁺, Fe³⁺ and Co²⁺, respectively. The calibration curves for flame AAS determination were linear in the ranges 0.018–1.0, 0.067–5.0, 0.2–5.0, 0.9–20, 0.028–2.0, 0.077–5.0, 0.19–10 and 0.1–3.5µgmL^–1, respectively. All the eight metal ions in river and synthetic water samples, Co in vitamin tablets and Zn in milk samples have been quantitatively enriched with Amberlite XAD-2-DHP and determined by flame atomic absorption spectrometry.     

Λ-、△-[Rh（bpy）2chrysi]^3＋对含C：T错配的DNA序列识别作用的分子模拟研究

通过分子模拟方法研究了手性金属配合物[Rh（bpy）2Chrysi]^3＋（bpy=2，2’-bipyridineChrysi=5，6-chrysenequinonediimine）对包含C：T错配碱基对的B-DNA序列的识别作用．结合类似的针对含G：A错配的和正常的B-DNA序列的识别作用研究，发现配合物I-Rh（bpy）zChrysi]^3＋可以对错配B-DNA序列进行序列特异性的识别．能量对比计算结果表明，该经典插入识别作用倾向于在错配碱基对附近进行，其中△-[Rh（bpy）2chrysi]^3＋比其手性异构体更占优势．这同Barton教授工作组的实验结果是一致的．另外插入作用倾向于在错配序列中的正常双碱基对C3A4／G3T4（错配碱基对附近）中从小沟进行．与该配合物对含G：A错配的和正常的B-DNA序列的识别作用不同的是，对包含C：T错配碱基对的B-DNA序列的识别作用倾向于从小沟进行．这一点可能源于C：T碱基对结构的不同．