Synthesis and structure of complex compound Rh(III) of (NH4)2[Rh(NO2)3(NH3)(µ-OH)]2 composition

The crystalline structure of a new compound Rh(III) of (NH₄)₂[Rh(NO₂)₃(NH₃)(μ-OH)]₂ composition has been determined. The crystallographic characteristics are H₁₆N₁₀O₁₄Rh₂: a = 6.3963(2) Å, b = 9.3701(4) Å, c = 13.6646(5) Å, β = 102.266(1)°, V = 800.28(5) ų, Z = 2, d _calc = 2.432 g/cm³. The distance Rh...Rh in the dimer is 3.200 Å. Original Russian Text Copyright ? 2006 by S. P. Khranenko, I. A. Baidina, and S. A. Gromilov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 47, No. 2, pp. 380–384, March–April, 2006.     

四氮杂环十二烷铒配合物的合成及其晶体结构

氮气保护下, 在无水乙腈中合成了1, 4, 7, 10-四氮杂环十二烷(Cyclen)与稀土铒的配合物并得到浅红色棱柱状晶体。元素分析结果表明该配合物的组成为Er(Cyclen)(CF3SO3)3(CH3CN)。用X射线衍射方法研究了其单晶结构。晶体属单斜晶系, P21/a空间群。晶胞参数为a=1.7335(4), b=1.8027(4),c=0.8772(3)nm, β=97.64(3)°, V=2.7171(2)nm^3, Z=4。其中铒为八配位,形成四方反棱柱型配位多面体。     

Double complex salts [Ni(NH3)6]3[Fe(CN)6]2 and [Ni(NH3)6]3[Cr(CNS)6]2: Synthesis and properties

The double complex salts [Ni(NH₃)₆]₃[Fe(CN)₆]₂ and [Ni(NH₃)₆]₃[Cr(CNS)₆]₂ were synthesized and their thermal decomposition in air was studied. The values of interplanar distances in crystal lattices were determined. The compounds are proposed as precursors for producing homogeneous bimetallic nanodimensional powders.     

First characterization of the ammine-ammonium complex [(NH4(NH3)4)2(mu-NH3)2]2+ in the crystal structure of [NH4(NH3)4][B(C6H5)4].NH3 and the [NH4(NH3)4]+ complex in [NH4(NH3)4][Ca(NH3)7]As3S6.2NH3 and [NH4(NH3)4][Ba(NH3)8]As3S6.NH3

The compound [NH4(NH3)4][B(C6H5)4].NH3 (1) was prepared by the reaction of NaB(C(6)H(5))(4) with a proton-charged ion-exchange resin in liquid ammonia. [NH(4)(NH(3))(4)][Ca(NH(3))(7)]As(3)S(6).2NH(3) (2) and [NH4(NH3)4][Ba(NH3)8]As3S6.NH3 (3) were synthesized by reduction of As(4)S(4) with Ca and Ba in liquid ammonia. All ammoniates were characterized by low-temperature single-crystal X-ray structure analysis. They were found to contain the ammine-ammonium complex with the maximal possible number of coordinating ammonia molecules, the [NH4(NH3)4]+ ion. 1 contains a special dimer, the [(NH4(NH3)4)2(mu-NH3)2]2+ ion, which is formed by two[NH4(NH3)4]+ ions linked by two ammonia molecules. The H(3)N-H...N hydrogen bonds in all three compounds range from 1.82 to 2.20 A (DHA = Donor-H...Acceptor angles: 156-178 degrees). In 2 and 3, additional H(2)N-H...S bonds to the thioanions are observed, ranging between 2.49 and 3.00 A (DHA angles: 120-175 degrees). Two parallel phenyl rings of the [B(C(6)H(5))(4)](-) anion in 1 form a pi...pi hydrogen bond (C...C distance, 3.38 A; DHA angles, 82 degrees), leading to a dimeric [B(C6H5)4]2(2-) ion.     

配合物[Fe(OPPh3)4Cl2][FeCl4]的合成和晶体结构

亚砜（R2SO4）是四价有机硫化合物中最重要的一类化合物,它的还原产物R2S可作为配体与过渡金属离子配位,从而得到许多结构新颖的化合物。这类反应一般在金属离子Os^11、Ru^11、Pt^11和Re^Vi等存在下发生,但很少出现在Fe^Ⅲ离子上。本文首次利用FeCl3、PPh3和DMSO反应,得到标题配合物并测定了其晶体结构。     

Preparation,characterization and cytotoxic activity of new compounds trans-[PtCl2NH3(3-(hydroxymethyl)-pyridine)] and trans-[PtCl2NH3(4-(hydroxymethyl)-pyridine)]

We report the synthesis, characterization and cytotoxic assays of new trans-platinum compounds, trans-[PtCl₂NH₃(3-(hydroxymethyl)-pyridine)] and trans-[PtCl₂NH₃(4-(hydroxymethyl)-pyridine)]. In the present work, we found that the replacement of the ammine ligand in “classical” transplatinum with the two new ligands does not increase the cytotoxic activity, maybe because these complexes do not produce a stability of the intrastrand cross-links in DNA.     

Synthesis and structure of the new complex hydride Li2BH4NH2

The structure of the new complex hydride Li(2)BH(4)NH(2), determined through Rietveld analysis of synchrotron X-ray and neutron powder diffraction data, comprises a hexagonal array of discrete (LiNH(2))(6) clusters dispersed in a LiBH(4) matrix.     

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.     

Synthesis,crystal, molecular,and electronic structure of [ReOCl3(bpzm)] complex

The [ReOCl₃(OAsPh₃)(AsPh₃)] and [ReOCl₃(PPh₃)₂] complexes react with bis(pyrazol-1-yl)methane (bpzm) to give [ReOCl₃(bpzm)]. The compound has been studied by IR, UV–Vis spectroscopy, and X-ray crystallography. The molecular orbital diagram of the oxocomplex has been calculated with the density functional theory (DFT) method. The spin-allowed singlet–singlet electronic transitions of [ReOCl₃(bpzm)] have been calculated with the time-dependent DFT method, and the UV–Vis spectrum of the title compound has been discussed on this basis.     

Synthesis and structure of a platinum-palladium complex [η3-C3H5Pd(μ-OAc)2PtPPh3(OAc)]

Conclusions A novel type of platinum-palladium heteronuclear complex containing bridging acetate ligands, namely, (³-allyl)palladium(II)triacetatotriphenylphosphine) platinum(II), has been prepared by reaction of bis[³-allyl)chloropalladium] with triacetatoargento(I)triphenyl-phosphineplatinum(II); the complex was characterized on the basis of x-ray structural analysis, and its IR, PMR, and³¹P-NMR spectral data.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1894–1897, August, 1988.     

Synthesis,crystal structure and magnetic properties of a two-dimensional mixed-valence assembly [Fe(salen)]2[Fe(CN)5NO]

A cyanide-bridged Fe^III–Fe^II mixed-valence assembly, [Fe^III(salen)]₂[Fe^II(CN)₅NO] [salen = N,N-ethylenebis(salicylideneiminato)dianion], prepared by slow diffusion of an aqueous solution of Na₂[Fe(CN)₅NO] · 2H₂O and a MeOH solution of [Fe(salen)NO₃] in an H tube, has been characterized by X-ray structure analysis, i.r. spectra and magnetic measurements. The product assumes a two-dimensional network structure consisting of pillow-like octanuclear [—Fe^II—CN—Fe^III—NC—]₄ units with dimensions: Fe^II—C = 1.942(7) Å, C—N = 1.139(9) Å, Fe^III—N = 2.173(6) Å, Fe^II—C—N = 178.0(6)°, Fe^III—N—C = 163.4(6)°. The Fe^II—N—O bond angle is linear (180.0°). The variable temperature magnetic susceptibility, measured in the 4.8–300 K range, indicates the presence of a weak intralayer antiferromagnetic interaction and gives an Fe^III–Fe^III exchange integral of –0.033 cm^–1.     

Synthesis,characterization and some reactions of trans-[Co(NH3)4(CH3NH2)Br]2+ and trans-[Co(NH3)4(CH3NH2)(NO3)]2+ complexes

The preparation of trans-[Co(NH₃)₄(CH₃NH₂)Br]²⁺ and trans-[Co(NH₃)₄(CH₃NH₂)-(NO₃)]²⁺ complexes is described. The UV-VIS spectra of the complexes indicate a decrease of the ligand field compared to the parent pentaammines. Infrared spectra match with the pattern of the corresponding pentaammines. The catalyzed (by Hg²⁺) aquation of the trans-bromomethylamine complex go under retention of the stereochemical configuration. The base hydrolysis (studied at 25°C) products show trans to cis rearrangement for both complexes. ¹H NMR spectroscopy is used for identification of the stereochemical configuration of the compounds.     

Synthesis and X-ray crystal structure of [Et4N] [Co(NH2-CSNHNH2)3] [Mo8O26]·4Me2NCHO

Summary [Et₂N] [Co(NH₂CSNHNH₂)₃] [Mo₈O₂₆] ·4Me₂NCHO, obtained by reacting MoCl₅, CoCl₂, thiosemicarbazide and DMF in nonaqueous solvents under i.r. radiation, was characterized by spectroscopy and X-ray crystallography. It contains an octanuclear molydenum anion with two pentabridging oxygen atoms and a cobalt-centred cation bonded to nitrogen and sulphur ligands.     

Crystal structure and NMR study of a bisperoxovanadium complex [NH4][VO(O2)2(ima)]

A novel bisperoxovanadium complex, [NH₄][VO(O₂)₂(ima)] (1) (ima = imidazole-4-carboxamide), was synthesized by the reaction of NH₄VO₃ and ima in the presence of H₂O₂, and the structure was characterized by single-crystal X-ray technology. The adjacent [NH₄][VO(O₂)₂(ima)] monomers further constructed a 3-D supramolecular framework through intra- and intermolecular hydrogen bonding interactions. The composition of the title complex solution was explored using a combination of multinuclear (¹H, ¹³C and ⁵¹V) magnetic resonance, heteronuclear single quantum coherence (HSQC), and variable temperature NMR in a 0.15 mol L^?1 NaCl/D₂O solution that mimics physiological conditions. According to NMR experimental results, a pair of isomers (Isomers A and B) are observed in aqueous solution, which are attributed to different types of coordination modes between the metal center and the ligands; Isomer B (the main product) has the same coordination structure as the crystal structure of [NH₄][VO(O₂)₂(ima)]. The ⁵¹V NMR experiment together with single-crystal X-ray diffraction results indicated that Isomer A is the hexa-coordinated peroxovanadium species while Isomer B is the hepta-coordinated species.     

[CrBr2(NH3)4][CrBr4(NH3)2], a new chromium(III) complex

Green single crystals of trans‐tetraamminedibromidochromium(III) trans‐diamminetetrabromidochromate(III), [CrBr₂(NH₃)₄][CrBr₄(NH₃)₂], are found to contain two symmetry‐independent sixfold coordinated Cr^III cations on centres of inversion. The structure is composed of octahedral trans‐[CrBr₂(NH₃)₄]⁺ cations and octahedral trans‐[CrBr₄(NH₃)₂]⁻ anions, and adopts a distorted CsCl‐type lattice. The cations and anions are linked by N—H...Br interactions. This is the first example in which both ions are mixed ammine–bromide Cr^III complexes.     

Darstellung und Charakterisierung der Pentammin-Komplexe [Os(NH3)5(NCS)]2+ und [Os(NH3)5(NCSe)]2+

Preparation and Characterization of the Pentammine Complexes [Os(NH₃)₅(NCS)]²⁺ and [Os(NH₃)₅(NCSe)]²⁺ The new pentammine complexes [Os(NH₃)₅(NCS)]²⁺ and [Os(NH₃)₅(NCSe)]²⁺ are prepared from the reaction of [Os(NH₃)₅(CF₃SO₃)](CF₃ SO₃)₂ with NH₄SCN and KSeCN, respectively, in acetone, and subsequent purification by ion exchange chromatography on carboxymethyl cellulose. Evidence of N-bonding in both cases is given by the vibrational spectra, indicating that Os³⁺ is in terms of Lewis acidity harder than Ru³⁺, Rh³⁺, and Ir³⁺. I.r. and Raman spectra are interpreted according to local C_4v symmetry around Os, and the presumed assignments are confirmed by comparison with the i.r. spectra of the perdeuterated compounds. In the electronic spectra of both complexes charge transfer bands at 412 nm (NCS) and 498 nm (NCSe) are observed, respectively. Further weak absorptions near 4500 and 5100 cm^?1, which are in correlation with electronic Raman bands, are assigned to intraconfigurational transitions within the ²T_2g (O_h) ground term, split into three Kramers doubletts by spin-orbit coupling and lowered symmetry. Electrochemical measurements demonstrate a stabilisation of +III and +II oxidation states by π-back donation to —NCS and —NCSe ligands.     

Crystal structure and fluorescence spectrum of the complex [Eu(III)(TTA)3(phen)]

The title complex Eu(III)(TTA)₃(phen) (where TTA = thenoyltrifluoroacetone monoanion; phen = 1,10-phenanthroline) has been synthesized in mixed solvents of acetone and ethanol (1:1 volume ratio) and its crystal structure has been determined by X-ray diffraction. The complex crystals are triclinic, space group P 1 (# 2) with cell dimensions of a = 1.32.41 (2) nm, b = 1.5278(4) nm, c = 0.9755(3) nm, α = 92.49 (2)°, β = 102.57(2)°, γ = 91.62(2)°, V = 1.9268(8) nm³, Z = 2, μ (Mo Ka)= 18.77 cm^?1, D_x=1.720 g/cm³. The coordination geometry of Eu atom is a distorted square antiprism, and the encapsulated structure that can meet the structural requirement of the typical europium luminescent sensor. The fluorescence spectrum suggests that the complex is a strong photoluminescent material.