Influence of the Coordination of Donor Solvent Molecules to 1,4,7,10-Tetramethyl-1,4,7,10- tetraazacyclododecanenickel(II) and Analogous Nickel(II) Complexes on Their Steric Factors

Coordination equilibrium constants (K _NiS) of some donor solvent molecules to 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecanenickel(II) ([Ni(Me₄[12]aneN₄)]²⁺) were determined in nitrobenzene (a noncoordinating bulk solvent). The first (K _NiS1) and second stepwise coordination equilibrium constants (K _NiS2) for 1,4,7,10-tetraazacyclododecanenickel(II) ([Ni([12]aneN₄)]²⁺), 1,4,8,11-tetraazac yclotetradecane- nickel(II) ([Ni([14] aneN₄)]²⁺), 1,4,8,11-tetrathiacyclotetra-decanenickel(II) ([Ni([14]aneS₄)]²⁺) were also reinvestigated. The K _NiS values for [Ni(Me₄[12]aneN₄)]²⁺ were compared to those of [Ni([12]aneN₄)]²⁺, (1R,4S, 8R,11S)-1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecanenickel(II) (R,S,R,S-[Ni(Me₄[14]aneN₄)]²⁺), R,R,S,S-[Ni(Me₄[14]aneN₄)]²⁺, [Ni([14]aneN₄)]²⁺, and [Ni([14]aneS₄)]²⁺. Coordination of pyridine (Py), N,N,N′,N′-tetramethylurea (TMU), and N,N-dimethylacetamide (DMA) to [Ni(Me₄[12]aneN₄)]²⁺ was observed, although these donor solvent molecules did not coordinate to R,S,R,S-[Ni(Me₄[14]aneN₄)]²⁺. The K _NiS values for Py, TMU, and DMA are 7.9, 2.8, and 9.0 dm³⋅mol⁻¹, respectively. Some hydrogen-bonding waters were coordinated to R,S,R,S-[Ni(Me₄[14]aneN₄)]²⁺, but such waters did not coordinate to [Ni(Me₄[12] aneN₄)]²⁺. Also, the K _NiS2 values were larger than the corresponding K _NiS1 values for [Ni([14]aneS₄)]²⁺. Furthermore, the K _NiS1 values for [Ni([12]aneN₄)]²⁺ were the largest among these nickel(II) complex cations. The K _NiS, K _NiS1, and K _NiS2 values are discussed in terms of properties of the donor solvents and steric strains of these nickel(II) complex cations.     

三(2-氨基乙基)胺-镉(Ⅱ)-2-甲基咪唑三元配合物的合成、结构与抗微生物活性

The complex [Cd(tren)(meim)](ClO₄)₂ was synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The compound crystallizes in monoclinic system, space group P2₁/m with a=0.786 8(2) nm, b=0.834 2(2) nm, c=1.496 2(4) nm, M_r=538.64, Z=2, F(000)=542, D_c=1.822 g·cm^-3, T=298(2) K, μ=1.435 mm^-1 and λ=0.071 073 nm. The structure was refined to R=0.045 8 and wR=0.123 1 for 1 489 observed reflections with I>2σ(I). The complex was valued for its antimicrobial activity against bacterial strands using the agar diffusion method. It was found to be active against the four test bacterial organisms. CCDC: 600198.     

稀土含硫有机配体配合物的合成与应用研究进展

简要综述了稀土含硫有机配体配合物的常用合成方法, 概述了该类型配合物在橡胶硫化、摩擦学、稀土农用和医药等领域的潜在应用, 并指出了稀土含硫配合物今后的研究重点.     

Crystallization of Two Cyanide-bridged Bimetallic Complexes [LN(DMSO)2(H2O)3Co(CN)6]·H2O (LN = Pr or Nd, DMSO = Dimethylsulfoxide)

1INTRODUCTIONRecently,therehasbeenconsiderableinterestinthelanthanide(III)hexacyanoferrates,theanalogoushexacyanocobaltateandhexacyanochromiumatecom-plexesbecauseoftheirpotentialapplicationsascata-lyticandsemi-conductivematerials.InitialstudiesofmetalhexacyanocobaltateswerecarriedoutbyJa-mesandWilland[1]whoreportedtheamountofhy-drationassociatedwithmicroscopiccrystalsofsever-allanthanidecomplexes.FurtherBonnetandParis[2]studiedtheLNCo(CN)6?nH2Oseries(n=4)byusinginfraredandX-raymethod…     

Synthesis of N—（4—Salicylideneiminoaryl）monoaza Crown Ethers and Dioxygen Affinities of Their Cobalt（Ⅱ）Complexes

The Schiff base‐containing pendant monoaza crown ether HL¹, HL², HL³ and HL⁴ have been synthesized by condensation of salicylaldehyde with N‐(4‐aminoaryl) monoaza crown ethers, which were prepared conveniently from 4‐nitro‐N, N‐di(hydroxyethyl) aniline or 4‐nitrobenzyl chloride via cyclization or condensation and reduction. The structures of HL¹—HL⁴ were verified by ¹H NMR, IR spectra, MS and elemental analysis. Moreover, the oxygenation constants (KO2) and thermodynamic parameters (δH⁰ and δS⁰) of their cobalt(II) complexes were determined in the range of ?5 °C to 25 °C, and the effect of crown ring bonded to a Schiff base on the dioxygen affinities of cobalt(II) complexes was also observed as compared to the uncrowned analogue (CoL).     

Structural investigation of dibromobis(benzimidazole)Zn(II) complex

The molecular structure of the title complex [ZnBr₂(C₇H₆N₂)₂] was investigated by X-ray diffraction and IR spectroscopy methods. Molecules of zinc(II) complex crystallize in the triclinic crystal system with cell constants a=7.526(2) Å, b=7.8971(8) Å, c=13.431(1) Å, Z=2 and V=791.3(2) Å³. In the molecular structure, the Zn atom is coordinated tetrahedrally by two Br⁻ anions and two benzimidazole ligands. Intramolecular steric repulsions between Br⁻ anions and benzimidazole groups have been caused to cis configuration around the central metal atom.     

电磁波对化学反应非致热作用的实验研究

微波加快化学反应速度除微波对反应物的加热以外还有非致热的作用，本文用实验证实了电磁波对离子和极性分子的洛仑兹力的作用导致了指前因子和活化能的变化，并提出用电磁作用因子描术电磁波对化学反应作用的大小。     

New transformations of vinyl acetate under the influence of the complex Rh(PPh3)3Cl

The strictly regioselective hydrocarboxylation of vinyl acetate to ethylidene diacetate by acetic acid formed in situ from vinyl acetate was realized for the first time with Rh(PPh₃)₃Cl as catalyst. The transformation of vinyl acetate into benzene, acetophenone, and acetylene was also realized.Institute of Organic Chemistry, Urals Branch, Russian Academy of Sciences, 420083 Ufa. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1406–1408, June, 1992.     

Zur Reaktion von Makrozyklen mit Lanthanoiden. I. Die Struktur von [Li(thf)][(C22H22N4)2Ce] · THF

On the Reaction of Macrocycles with Lanthanoids. I. The Crystal Structure of [Li(thf)][(C₂₂H₂₂N₄)₂Ce] · THF In THF CeBr₃ forms with [(TMTAA)Li₂] the paramagnetic doubledecker complex [Li(thf)][(TMTAA)₂Ce]. The complex crystallizes with 1 Mol THF per formula unit. The structure was characterized by X-ray single crystal structure analysis (space group C2 (No. 5), z = 6, a = 1741.8(2) pm, b = 1622.1(2) pm, c = 2540.4(3) pm, β = 104.72(1)°). The sandwich-like arrangement of the heterocyclic ligands leads to a quadratic-prismatic coordination of the Ce³⁺ ion. One macrocyclic ligand is additionally coordinated by a [Li(thf)]⁺ fragment. The coordination of the Li ion is square pyramidal.     

Synthesis and transformations of metallacycles 33. The first example of cycloalumination of cyclonona-1,2-diene with Et<Subscript>3</Subscript>Al and EtAlCl<Subscript>2</Subscript> in the presence of Cp<Subscript>2</Subscript>ZrCl<Subscript>2</Subscript>

Catalytic cycloalumination of cyclonona-1,2-diene upon treatment with Et₃Al and EtAlCl₂ in the presence of Cp₂ZrCl₂, leading to 10-ethyl-10-aluminabicyclo[7.3.0^1,9]dodec-8-ene (1) and 11-ethyl-11-aluminatricyclo[10.7.0^1,12.0^2,10]nonadeca-9,12-diene, respectively, was accomplished in high yields. A possibility for the selective transformation of compound 1 to 1-allyl-9-(pent-4-enyl)cyclonon-1-ene and 10-hydroxybicyclo[7.3.0^1,9]dodec-8-ene in one preparative step was demonstrated. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2156–2159, November, 2007.