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Vol 42, No 12 (2016)
- Year: 2016
- Articles: 7
- URL: https://journals.rcsi.science/1070-3284/issue/view/13280
Article
Electrochemical and chemical syntheses, structures, and optical properties of the zinc and cadmium complexes in the N,N,O,S-ligand environment
Abstract
The chemical and electrochemical syntheses of the zinc (I) and cadmium (II) complexes are carried out on the basis of the tridentate Schiff base (H2L), the condensation product of (2-tosylaminoaniline) N-(2-aminophenyl)-4-methylbenzenesulfunamide with 1-phenyl-3-methyl-4-formylpyrazole-5-thiol. The structures and compositions of the synthesized metallochelates are proved by the data of C, H, and N elemental analyses, IR spectroscopy, and 1H NMR spectroscopy. X-ray absorption spectroscopy is used to determine the structure of the zinc complex. The binuclear structure of the cadmium complex is confirmed by the X-ray diffraction data (CIF file CCDC no. 1471159). The optical properties of H2L and the zinc and cadmium complexes in dimethyl sulfoxide (DMSO) solutions are studied.
755-762
Crystal structure of the CuCl2 complex with two molecules of N',N'-dimethyl-para-tert-butylbenzohydrazide [Cu(p-(t-Bu)C6H4CONHN(Me)2)2]Cl2 ∙ 1.34 Н2О
Abstract
Complex [Cu(HL1)2]Cl2 ⋅ 1.34 Н2О (HL1 = p-(t-Bu)C6H4CONHN(Me)2) is studied by X-ray diffraction analysis. The coordination polyhedron of the copper atom is a distorted tetragonal pyramid, whose base is formed by the amine N and O atoms of two ligands HL1, and one of the chlorine atoms occupies the vertex. The second chlorine atom does not enter into the coordination sphere of copper but is linked through an intramolecular hydrogen bond with the NH group. Reagent HL1 forms a five-membered metallocycle with the central atom. The metallocycle exists in an envelope conformation with the copper atom in the flap. CIF file CCDC no. 1453151.
763-767
Synthesis, some properties, and crystalline modifications of fac-[Ru(NO)(Py)2Cl3]
Abstract
According to the data of 1H NMR spectroscopy, trans-hydroxochloro complexes containing from two to four pyridine molecules in the internal sphere are formed on the heating of a dilute aqueous solution of K2[Ru(NO)Cl5] with pyridine. The evaporation of the reaction solution with concentrated hydrochloric acid gives fac-[Ru(NO)(Py)2Cl3] (I) in a yield of ~90%. The structures of two crystalline modifications of this complex are determined by X-ray diffraction analysis (CIF files ССDС nos. 1452208 (Ia) and 1452207 (Ib)). IR spectroscopy shows that the irradiation of complex I (λ ~ 450 nm, T = 80 K) results in photoisomerization with the formation of the metastable state MS1 in which the nitroso group is coordinated by the oxygen atom. The activation parameters of the photoisomerization are determined from the data of differential scanning calorimetry (DSC). Compound trans-[Ru(NO)Py4(OH)]Cl2 ∙ H2O is isolated in a yield of ~70% on reflux of complex I with a pyridine excess in an aqueous solution, and the presence of molecules of water of crystallization in this compound is confirmed by thermal gravimetry (TG) and IR spectroscopy.
768-774
The formation of nickel(II) chloride ammine complexes in the pores of modified fibers of cellulose cloth
Abstract
A sorbent was synthesized as a cellulose cloth, the fibers of which have nanopores with walls made of cellulose chains and ethanol cyclams. The formation of (NH4)2[NiL(NH3)2Cl2] complexes where L2– is the CH–(O–)–CH–(O–) glucopyranose group was established by chemical analysis and IR and UV/Vis spectroscopy. Using small-angle X-ray scattering and measurement of the partial free space and adsorption capacity, the complex formation in the [Ni(NH3)6]Cl2 concentration range of up to 0.43 mol/L was found to occur in nanopores with the sorption constant Ksorb = 15.8. The limiting content of the complexes is 2.63 mmol/g and their effective radius is 0.45 nm. In the concentration range of 0.43–0.91 mol/L, the complexation occurs on the fiber surface, Ksorb = 1.85. The effective radius of the complexes is 0.5 nm.
775-778
Synthesis and structure of the rhodium complex [p-Tol4Sb(DMSO-O)]2+[trans-RhBr4(DMSO-S)2]–[cis-RhBr4(DMSO-S)2]–
Abstract
The complex [p-(Tol)4Sb(DMSO-O)2+[trans-RhBr4(DMSO-S)2]–[cis-RhBr4(DMSO-S)2]– (CIF file CCDC no. 1415243) was synthesized by the reaction of sodium hexabromorhodate with tetra(para-tolyl) stibonium bromide in DMSO and studied by X-ray diffraction. The antimony atoms in two types of crystallographically independent [p-Tol4Sb(DMSO-O)]+ cations have a distorted trigonal-bipyramidal coordination with axially arranged DMSO oxygen atoms (Sb–C, 2.088(9)–2.135(10) Å; Sb∙∙∙O, 2.641(10), 2.690(10) Å). In the octahedral [trans-RhBr4(DMSO-S)2]– and [cis-RhBr4(DMSO-S)2]– anions, the dimethyl sulfoxide ligands are coordinated to the metal via the sulfur atoms. The Rh–S distances are longer in the trans-isomer (2.333(2), 2.339(2) Å) than in the cis-isomer (2.303(3), 2.318(4) Å).
779-782
Reactivity of dinuclear ruthenium complex containing two 1,2-dicarba-closo-dodecaborane-1,2-dithiolate ligands toward HC≡CCH(OH)(CH3)2
Abstract
The reaction of (p-cymene)Ru2(μ-S2)(S2C2B10H10)2 (I) with HC≡CCH(OH)(CH3)2 in dichloromethane led to addition complexes, (p-cymene)Ru2(μ-S2)(S2C2B10H10)2(R1C=CR2) (R1 = H, R2 = C(OH)(CH3)2 (II); R1 = C(OH)(CH3)2, R2 = H (III)). In boiling chloroform both complexes II and III spontaneously lose water to generate two geometrical isomers (p-cymene)Ru2(μ-S2)(S2C2B10H10)2(R1C=CR2) (R1 = H, R2 = C(CH3)=CH2 (IV); R1 = C(CH3)=CH2, R2 = H (V)), respectively. Complexes IV and V could be interconverted in boiling toluene. All these complexes were characterized by elemental analysis, mass spectrometry, and NMR spectroscopy. The molecular structure of complex IV has been determined by X-ray crystallography (CIF file CCDC no. 1443964). Complex IV crystallizes in monoclinic system, space group P21/c with a = 10.3717(9), b = 20.3982(17), c = 18.6428(13) Å, β = 111.096(4)°, C19H40B20Ru2S6, Mr = 879.27, V = 3679.8(5) Å3, ρc = 1.587 g/cm3, Z = 4, F(000) = 1752, μ(MoKα) = 1.179 mm–1, R = 0.0416 and wR = 0.0848 for 4602 observed reflections (I > 2σ(I)).
783-788
Three metal complexes based on tetrazolyl ligands: Hydrothermal syntheses, crystal structures, and fluorescence properties
Abstract
Three new complexes based on 1-tetrazole-4-imidazole-benzene (Tibz), namely, [Cd(Tibz)2(H2O)2]n (I), [Mn(Tibz)2(H2O)4] · 2H2O (II) and [Co(Tibz)2(H2O)4] · 2H2O (III) have been synthesized through hydrothermal method and structurally characterized by element analyses, IR spectroscopy and single-crystal X-ray diffraction analyses (CIF files CCDC nos. 1443867 (I), 1443868 (II), 1443869 (III)). Single-crystal X-ray diffraction reveals that complex I is a 1D double-chain architecture, II and III are both mononuclear complexes. The results of single-crystal X-ray diffraction analyses indicate that the hydrogen bond and π··· π stacking exist in the complexes, which make great contribution to the stabilities of complexes I–III. The fluorescent properties of these complexes have also been studied in the solid state at room temperature.
789-796