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Tyulyaeva E. Yu. Lomova T. N. Mozhzhukhina E. G. 《Russian Journal of Coordination Chemistry》2003,29(8):564-568
The Ru(IV) and Os(II) complexes (PhO)2RuTPP and OsTPP were synthesized from tetraphenylporphine (H2TPP) and K2RuO4 or K2OsO4 (taken in the molar ratio of 1 : 30) in boiling phenol. The kinetics of oxidation reactions of these complexes in solutions of HOAc (acetic), H2SO4, and HOAc–H2SO4 acids was studied. It was found that in the aerated HOAc–H2SO4 mixture heated above 340 K, these complexes are oxidized with participation of different reaction sites: the Ru(IV) complex is oxidized at macrocycle to give the -radical-cation (PhO)2RuPP+, while in the Os(II) complex, the metal atom is oxidized to form the Os(III) complex. In the first case, the reaction follows the activation mechanism, whereas in the second case, the activation energy of the reaction is zero. 相似文献
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M. Sc. Florian S. Schendzielorz Dr. Markus Finger M. Sc. Christian Volkmann Dr. Christian Würtele Prof. Dr. Sven Schneider 《Angewandte Chemie (International ed. in English)》2016,55(38):11417-11420
Low‐valent osmium nitrides are discussed as intermediates in nitrogen fixation schemes. However, rational synthetic routes that lead to isolable examples are currently unknown. Here, the synthesis of the square‐planar osmium(IV) nitride [OsN(PNP)] (PNP=N(CH2CH2P(tBu)2)2) is reported upon reversible deprotonation of osmium(VI) hydride [Os(N)H(PNP)]+. The OsIV complex shows ambiphilic nitride reactivity with SiMe3Br and PMe3, respectively. Importantly, the hydrogenolysis with H2 gives ammonia and the polyhydride complex [OsH4(HPNP)] in 80 % yield. Hence, our results directly demonstrate the role of low‐valent osmium nitrides and of heterolytic H2 activation for ammonia synthesis with H2 under basic conditions. 相似文献
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Abbas Tarassoli Ziba Khodamoradpur 《Phosphorus, sulfur, and silicon and the related elements》2013,188(2):527-532
Abstract The reaction of bis(anilino)phosphine oxide (C6H5NH)2P(O)H, 1 with Bu2 nSnCl2 in the presence of an excess of triethylamine (TEA) in dry tetrahydrofurane (THF) yields the novel N,O-bonded tin complex Bu2 nSn[NPh(O)P(H)NPh(HNEt3)]2, 2. TEA is used as a base to deprotonate the phosphazane ligand and is separated as Et3NH+Cl?, whereas HTEA+ exists in the final product 2 and act as a charge balancing and H-bond structure–directing agent. This new compound has been fully characterized by means of IR, MS, and multinuclear (1H, 31P, and 119Sn NMR) spectroscopy. 相似文献
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Mixed Halogeno-Ethylendiamine Complexes of Osmium (III) and (IV) [OsCl4en] or [OsBr4en] and [OsCl4en]- or [OsBr4en]- are prepared by reaction of [Os(en-H)2en]Br2 with HCl or HBr. Whereas the chelate group behaves inert, the halogeno ligands become substituted easily, alltogether or partly. This enables the preparation of [OsI4en], of complexes of the type [OsClnBr4?en]-, n = 1–3, and of other compounds. The chemical properties and infrared spectra of the new complexes are discussed. 相似文献
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Gubanov A. I. Gromilov S. A. Korenev S. V. Venediktov A. B. Asanov I. P. 《Russian Journal of Coordination Chemistry》2002,28(12):864-866
A new method of synthesis of potassium hexabromoiridate(IV) was developed. This complex was studied using X-ray diffraction and elemental analyses and electronic absoprtion, IR, and Raman spectroscopy methods. Crystallographic parameters: a = 10.298(5) Å, V = 1092.1 Å3, Z = 4, space group Fm3m, (calcd) = 4.560 g/cm3; K2[PtCl6] structural type. The thermal decomposition of this salt in an inert atmosphere was investigated. 相似文献
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Fomenko I. S. Nadolinnyi V. A. Efimov N. N. Kokovkin V. V. Gushchin A. L. 《Russian Journal of Coordination Chemistry》2019,45(11):776-781
Russian Journal of Coordination Chemistry - The binuclear oxidovanadium(IV) complex [VO(Dbbpy)Cl(Ca)Cl(Dbbpy)VO] (I) is synthesized by the reaction of [VO(Dbbpy)(H2O)Cl2] (Dbbpy is... 相似文献
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Reactions of OsO4 with HSR (R=C6F5, C6F4H-4,) in refluxing ethanol afford [Os(SC6F5)3(SC6F4(SC6F5)-2)] (1) and [Os(SC6F4H-4)3(SC6F3H-4-(SC6F4H-4)-2)] (2), which involve the rupture of C-F bonds. At room temperature, the compound [Os(SC6F5)3(PMe2Ph)2] or [Os(SC6F5)4(PMe2Ph)] reacts with KOH(aq) in acetone, giving rise to [ Os(SC6F5)(SC6F4(SC6F4O-2)-2)(PMe2Ph)2] (3), through a process involving the rupture of two C-F bonds, while the compound [Os(SC6F4H)4(PPh3)] reacts with KOH(aq) in acetone to afford [Os(SC6F4H-4)2(SC6F3H-4-O-2)(PPh3)] (4), which also implies a C-F bond cleavage. Single-crystal X-ray diffraction studies of 1, 2, and 4 indicate that these compounds include five-coordinated metal ions in essentially trigonal-bipyramidal geometries, whereas these studies on the paramagnetic compound 3 show a six-coordinated osmium center in a distorted octahedral geometry. 19F, 1H, 31P{1H}, and COSY 19F-19F NMR studies for the diamagnetic 1, 2, and 4 compounds, including variable-temperature 19F NMR experiments, showed that these molecules are fluxional. Some of the activation parameters for these dynamic processes have been determined. 相似文献
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Aline B. Schons Jamille S. Correa Patricia Appelt Daiane Meneguzzi Mrio A. A. Cunha Carla Bittencourt Henrique E. Toma Fauze J. Anaissi 《Molecules (Basel, Switzerland)》2022,27(19)
The search for less expensive and viable products is always one of the challenges for research development. Commonly, the synthesis of coordination compounds involves expensive ligands, through expensive and low-yield routes, in addition to generating toxic and unusable residues. In this work, the organic ligand used is derived from the resin of a reforestation tree, Pinus elliottii var. elliottii. The synthesis method used Pinus resin and an aqueous solution of vanadium(III) chloride at a temperature of 80 °C. The procedure does not involve organic solvents and does not generate toxic residues, thus imparting the complex formation reaction a green chemistry character. The synthesis resulted in an unprecedented oxovanadium(IV)-bis(abietate) complex, which was characterized by mass spectrometry (MS), chemical analysis (CHN), vibrational (FTIR) and electronic spectra (VISIBLE), X-ray diffraction (XRD), and thermal analysis (TG/DTA). Colorimetric studies were performed according to the CIELAB color space. The structural formula found, consisted of a complex containing two abietate ligands, [VO(C20H29O2)2]. The VO(IV)-bis(abietate) complex was applied against microorganisms and showed promising results in antibacterial and antifungal activity. The best result of inhibitory action was against the strains of Gram-positive bacteria S. aureus and L. monocytogenes, with minimum inhibitory concentration (MIC) values of 62.5 and 125 μmol L−1, respectively. For Gram-negative strains the results were 500 μmol L−1 for E. coli; and 1000 μmol L−1 for Salmonella enterica Typhimurium. Antifungal activity was performed against Candida albicans, where the MIC was 15.62 μmol L−1, and for C. tropicalis it was 62.5 μmol L−1. According to the MFC analysis, the complex presented, in addition to the fungistatic action, a fungicidal action, as there was no growth of fungi on the plates tested. The results found for the tests demonstrate that the VO(IV)-bis(abietate) complex has great potential as an antimicrobial and mainly antifungal agent. In this way, the pigmented ink with antimicrobial activity could be used in environments with a potential risk of contamination, preventing the spread of microorganisms harmful to health. 相似文献
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Determination of the Stability Constants of Mixed Hexahalogeno Complexes of Osmium(IV) The individual and total stability constants of the complex series [OsXxY6?x]2?; X ≠ Y = Cl, Br, I; x = 0–6 are determined by radiometric measurements of the equilibrium concentrations of all compounds. The thermodynamical stability increases from the hexabromo- over the hexachloro- to the hexaiodo-complex. The total stability constants are in ratio of 1:5,2:1225. With the individual constants the equilibrium diagrams are calculated. The photometric determination of the cis/trans ratio in complexes with x = 2, 3, 4 gives the statistical distribution of the ligands in the octahedrons. The relationship between thermodynamical and kinetical data is discussed. 相似文献
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Chlorodibenzyltin (IV) complex with dithiomorpholinocarbamate ligand was synthesized by the reaction of dibenzyltin dichloride with dithiomorpholinocarbamate in 1:1 stoichiometry. The complex was characterized by elementary analysis, UV, BR and 1H NMR spectra. The crystal structure was determined by X‐ray single crystal diffraction study. The crystallographic data are as follows: triclinic, space group P1 , a = 0.8723 (2) ran, b = 1.099 (2) nm, c = 1.1036 (3) nm, α = 86.498 (4)°, β = 89.697 (5)°, γ = 82.807 (5)°, Z = 2, V = 1.0479 (4) nm3, Dc= 1.580 g/cm?3, μ = 1.553 mm?1, F (000) = 500, R1 = 0.0442, wR2 = 0.0974. The crystal consists of discrete molecules containing five‐coordinate tin atoms in a distorted tigonal bipyramidal configuration. The molecules are packed in the unit cell in one‐dimensional chain structure through a weak interaction between the chlorine atom and sulfur atom, the sulfur atom and one of the sulfurs of an adjacent molecule. 相似文献
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IntroductionBecausethepolynuclearcomplexes ,consistingofaromaticmulti carboxylicacidandtransitionmetal,haveavarietyofpossibleapplicationsrangingfromfineretar dantstocatalysts ,andpotentiallyvaluablepropertiesreminiscentofzeolites ,thestudyonthemhasbeenan… 相似文献
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The title complex [Ph3Sn(CH3OH) (terephthalate) (CH3OH) SnPh3]·2CH3OH was synthesized by the reaction of Ph3SnCl with terephthalate in the molar ratio of 2:1 in methanol solution and characterized by elemental analysis, IR and 1H NMR spectra, and the crystal structure was determined by X‐ray single crystal diffraction study. The crystal belongs to monoclinic with space group P21/n, a = 1.5199(5) nm, b = 0.9000(3) nm, c = 1.8206(6) nm, β= 113.970(5)°, Z = 2, V = 2.2755 (13) nm3, Dc= 1.413 g/cm3, μ = 1.146 mm?1, F(000) = 980, R =0.0353, wR = 0.0606. In the crystals of complex, the tin atoms rendered five‐coordinate in a distorted trigonal bipyramidal structure. 相似文献
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IntroductionOrganotin(IV)complexeswerewidelyusedasbio cides,fungicidesandinindustryashomogeneouscata lysts.1 6 Morerecently ,pharmaceuticalpropertiesofalkyltin(IV)complexeswithN ,N dialkyldithiocarba mateligandshavebeeninvestigatedfortheirantitumouractivity.7,8… 相似文献