Thermal behavior of some new complexes bearing ligands with polymerisable groups

This paper reports the investigation of the thermal stability of a series of new complexes with mixed ligands of the type M(dipy)(C₃H₃O₂)₂(H₂O)_y ((1) M: Mn, y=1; (2) M: Ni, y=2; (3) M: Cu, y=1; (4) M: Zn, y=2; dipy: 2,2’-dipyridine and C₃H₃O₂ is acrylate anion). The thermal behaviour steps were investigated. The thermal transformations are complex processes according to TG and DTG curves including dehydration, oxidative condensation of acrylate and thermolysis processes. The final products of decomposition are the most stable metal oxides.     

Some new acrylate complexes as a criterion in their selection for further co-polymerization reaction

Summary This paper reports the investigation of the thermal stability of a series of new complexes with mixed ligands of the type M(phen)(C₃H₃O₂)₂(H₂O)_y ((1) M=Mn, y=0; (2) M=Ni, y=2; (3) M=Cu, y=1; (4) M=Zn, y=2; phen=phenanthroline and C₃H₃O₂ is acrylate anion). The thermal behaviour steps were investigated. The thermal transformations are complex processes according to TG and DTG curves including dehydration, oxidative condensation of acrylate and thermolysis processes. The final products of decomposition are the most stable metal oxides.     

Thermal behavior of some new triazole derivative complexes

A series of new complexes with mixed ligands of the type [ML(C₃H₃O₂)₂]·nH₂O (((1) M=Mn, n=1; (2) M=Co(II), n=2; (3) M=Ni(II), n=4; (4) M=Cu(II), n=1.5; (5) M=Zn(II), n=0; L=3-amino-1,2,4-triazole and (C₃H₃O₂)=acrylate anion) were synthesized and characterised by chemical analysis and IR data. In all complexes the 3-amino-1,2,4-triazole acts as bridge while the acrylate acts as bidentate ligand except for complex (5) where it is found as unidentate. The thermal behaviour steps were investigated in nitrogen flow. The thermal transformations are complex processes according to TG and DTG curves including dehydration, acrylate ion and 3-amino-1,2,4-triazole degradation respectively. The final products of decomposition are the most stable metal oxides, except for complex (4) that leads to metallic copper.     

Thermal stability of new complexes bearing both acrylate and aliphatic amine as ligands

This paper reports the investigation of the thermal stability of a series of new complexes with mixed ligands of the type [M(en)(C₃H₃O₂)₂]·nH₂O ((1) M=Ni, n=2; (2) M=Cu, n=0; (3) M=Zn, n=2; en=ethylenediamine and (C₃H₃O₂)=acrylate anion). The thermal behaviour steps were investigated in a nitrogen flow. The thermal transformations are complex processes according to TG and DTA curves including dehydration, ethylenediamine elimination as well as acrylate thermolysis. The final products of decomposition are the most stable metal oxides except for complex (2) that generates metallic copper.     

Thermal decomposition of 4,4′-dipyridyl complexes of light rare-earth thiocyanates in air atmosphere

The thermal decompositions of Ln(NCS)₃(4-dipy)₂·5H₂O were studied, whereLn=La, Pr, Nd, Sm, Eu and Y, and 4-dipy=4,4′-dipyridyl. The compounds are first dehydrated. During the thermal decomposition of Ln(NCS)₃(4-dipy)₂, deamination takes place. The transient products decompose with the formation of Ln₂O₂SO₄. The energies of activation for the first step of dehydration of the La, Pr, Nd, Sm and Eu complexes were determined.

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Zusammenfassung Es wurde die thermische Zersetzung von Ln(NCS)₃(4-dipy)₂.5H₂O mitLn=La, Pr, Nd, Sm, Eu, Y und 4-dipy=4,4′-Dipyridyl untersucht. Die Verbindungen werden zuerst dehydratiert. Bei der thermischen Zersetzung von Ln(NCS)₃(4-dipy)₂ findet eine Desaminierung statt. Die übergangsprodukte zersetzen sich unter Bildung von Ln₂O₂SO₄. Die Aktivierungsenergie für den ersten Schritt der Dehydratation der La-, Pr-, Nd-, Sm- und Eu-Komplexe wurde ermittelt.

     

Oxo Peroxo Glycolato Complexesof Vanadium (V). Crystal Structureof (NBu4)2[V2O2(O2)2(C2H2O3)2]ċH2O

Summary.  Oxo peroxo glycolato complexes of vanadium(V) (M ₂[V₂O₂(O₂)₂(C₂H₂O₃)₂]ċnH₂O (n=0, 1; M=NBu₄ ⁺ (1), K⁺ (2), NH₄ ⁺ (3), Cs⁺ (4), NPr₄ ⁺ (5)) as well as (NBu₄)₂[V₂O₄(C₂H₂O₃)₂]ċ H₂O (6) have been prepared and characterized by spectroscopic methods. X-Ray structure analysis of 1 revealed the presence of dinuclear [V₂O₂(O₂)₂(C₂H₂O₃)₂]²⁻ anions with a (chemical structure) bridging core and six coordinated vanadium(V) atoms in a distorted pentagonal pyramidal array. Received July 12, 1999. Accepted (revised) October 28, 1999     

Oxo Peroxo Glycolato Complexesof Vanadium (V). Crystal Structureof (NBu4)2[V2O2(O2)2(C2H2O3)2]?H2O

 Oxo peroxo glycolato complexes of vanadium(V) (M ₂[V₂O₂(O₂)₂(C₂H₂O₃)₂]ċnH₂O (n=0, 1; M=NBu₄ ⁺ (1), K⁺ (2), NH₄ ⁺ (3), Cs⁺ (4), NPr₄ ⁺ (5)) as well as (NBu₄)₂[V₂O₄(C₂H₂O₃)₂]ċ H₂O (6) have been prepared and characterized by spectroscopic methods. X-Ray structure analysis of 1 revealed the presence of dinuclear [V₂O₂(O₂)₂(C₂H₂O₃)₂]²⁻ anions with a (chemical structure) bridging core and six coordinated vanadium(V) atoms in a distorted pentagonal pyramidal array.     

Tetraalkylammonium fluorooxoperoxovanadates

Summary Compounds crystallizing from theMOH-HF-V₂O₅-H₂O₂-H₂O (M=N(CH₃)₄, N(C₂H₅)₄, N(C₄H₉)₄) system have been characterized by elemental analysis, vibrational spectra, and X-ray powder patterns. Besides [N(CH₃)₄]₂[VO(O₂)₂F]·2H₂O (1) and [N(CH₃)₄]₃[V₂O₂(O₂)₄F] (2) which correspond to the known compoundsM ₂[VO(O₂)₂F] (M=K, NH₄, Cs) and (NH₄)₃[V₂O₂(O₂)₄F]·2H₂O, respectively, complexes of two new types have been obtained: [N(C₂H₅)₄]₂[V₂O_5–x (O₂) _x F₂]·H₂O(x0.25,3) and the first trinuclear peroxo complex of vanadium(V), [N(C₄H₉)₄]₂[V₃O₃(O₂)₄F₃]·6H₂O(4).

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Tetraalkylammonium-Fluorooxoperoxovanadate

Zusammenfassung Aus dem SystemMOH-HF-V₂O₅-H₂O₂-H₂O (M=N(CH₃)₄), N(C₂H₅)₄, N(C₄H₉)₄) kristallisierende Verbindungen wurden mittels Elementaranalyse, Schwingungsspektroskopie und Röntgendiffraktion charakterisiert. Neben [N(CH₃)₄]₂[VO(O₂)₂F]·2H₂O (1) und [N(CH₃)₄]₃][V₂O₂(O₂)₄F] (2), welche den bekannten VerbindungenM ₂[VO(O₂)₂F] (M=K, NH₄, Cs) und (NH₄)₃[V₂O₂(O₂)₄)F]·2H₂O entsprechen, wurden zwei neue Typen von Komplexen erhalten: [N(C₂H₅)₄]₂[V₂O_5–x (O₂) _x F₂]·H₂O (x0.25,3) und der erste dreikernige Peroxokomplex von Vanadium(V), [N(C₄H₉)₄]₂[V₃O₃(O₂)₄F₃]·6H₂O (4).

     

Thermal behaviour of new biological active cadmium mixed ligands complexes

This paper reports the investigation on the thermal stability of new complexes with mixed ligands of the type [Cd(NN)(C₃H₃O₂)₂(H₂O)_m]·nH₂O [(1) NN: 1,10-phenantroline, m = 1, n = 0; (2) NN: 2,2′-bipyridine, m = 0, n = 1.5 and (C₃H₃O₂): acrylate anion]. The IR data indicate a bidentate coordination mode for both heterocyclic amine and acrylate. The in vitro qualitative and quantitative antimicrobial activity assays showed that the complexes exhibited variable antimicrobial activity against planktonic as well as biofilm embedded Gram-negative (Escherichia coli, Klebsiella sp., Proteus sp., Salmonella sp., Shigella sp., Acinetobacter boumani, Pseudomonas aeruginosa), Gram-positive (Bacillus subtilis, Staphylococcus aureus) and fungal (Candida albicans) strains, reference and isolated ones from the hospital environment. The thermal behaviour steps were investigated in synthetic air flow. The thermal transformations are complex processes according to TG and DTA curves including dehydration, amine as well as acrylate thermolysis. The final products of decomposition are the most stable metal oxides.     

基于2-丙基-4，5-咪唑二甲酸的锰（Ⅱ）和铜（Ⅰ）配合物的合成、晶体结构及性质研究

采用水热法合成了2个化合物{[Cu₂（Hpimdc）（4,4’-bpy）]·H₂O}_n（1）和[Mn₃（C₈H₇N₂O₄）₂·6H₂O]_n（2）（H₃pimdc=2-丙基-4,5-咪唑二甲酸,4,4’-bpy=4,4’-联吡啶）,并对2个化合物进行了红外、元素分析、晶体结构和热稳定性分析。晶体结构分析发现化合物1之中的H₃pimdc和4,4’-bpy交替与铜(Ⅰ)配位形成一维链线性铜(Ⅰ)配合物。沿a轴和（100）面去观察,2个一维链分子通过游离水连接而形成1个“U”型拓扑结构。而化合物2通过2-丙基-4,5-咪唑二甲酸链与锰(Ⅱ)连接为三维的网状结构。沿b轴方向,三维结构中存在交替的左/右手螺旋状二维结构。     

The effect of Er(III) on the thermal behavior of azo (–N=N–) and azomethinic (–CH=N–) chromophores

This paper reports the investigation of the thermal stability of a series of new complexes with azo and azomethinic chromophores of the type [Er(HL)₂(H₂O)₂](HO); ((B) H₂L: o,o’-dihydroxy-azobenzene (A); (D) H₂L: N-(2-hydroxy-1-naphthalidene)aminophenol (C); (F) H₂L: N-(2-hydroxy-1-naphthalidene)anthranilic acid (E)). The complexes thermal behaviour steps were investigated and comparatively presented with those of corresponding ligand. The thermal transformations are complex processes according to TG and DTG curves including phenol elimination, oxidative condensation and thermolysis processes. The final product of complexes decomposition is Er₂O₃.     

Synthesis and structures of nickel(II) trimethylacetate dimers with coordinated diamines

Thermal decomposition of the tetranuclear nickel(II) complex Ni₄lη²-o-(NH₂)(NHPh)C₆H₄|₂(MeCN)₂(μ-OOCCMe₃)₄(η²-OOCCMe₃)₂ (I) under an inert atmosphere (o-xylene, 140 °C) was investigated. Under these conditions, the asymmetric binuclear complex Ni|η²-o-(NH₂)(NHPh)C₆H₄‖(η¹-o-(NH₂))(NHPh)C₆H₄|(η²,η-O,O-OOCCMe₃)(η²-OOCCMe₃) (2) was formed at the first stage. Complex2 was converted into the symmetric dimer Ni|η¹-o-(NH₂)(NHPh)C₆H₄|(μ-OOCCMe₃)₄ (3) upon recrystallization from benzene. The structures of complexes2 and3 were established by X-ray diffraction analysis. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1915–1918, November, 2000.     

Reactions of pyridyl side chain functionalized cyclopentadiene with ruthenium carbonyl

Abstract  

Reactions of the pyridyl side-chain-functionalized cyclopentadiene [C₅H₅CR₂(CH₂C₅H₄N)] [R ₂ = Et₂ (1), (CH₂)₄ (2)] with Ru₃(CO)₁₂ in refluxing xylene gave the new intramolecular C–H activated trinuclear product [μ-(C₅H₃N)CH₂C(C₂H₅)₂(C₅H₄)Ru(CO)]₂Ru(CO)₂ (3) and the normal dinuclear metal complex [(C₅H₄N)CH₂C(CH₂)₄(C₅H₄)Ru(CO)]₂(μ-CO)₂ (4). The structures of the trinuclear complex 3 and dinuclear complex 4 were characterized by elemental analysis, IR spectra, ¹H-NMR and X-ray diffraction.     

Crystal structures and magnetic interactions in nickel(II) dibridged complexes formed by both phenolate oxygen-azide,or methanlate groups

Abstract  

Tridentate Schiff base ligands L¹ and L², derived from the condensation of 2-hydroxy-3-methoxybenzaldehyde (L) with 2-aminoethanol or 2-aminobutan-1-ol, react with nickel chloride, azide, or thiocyanate to give rise to two dinuclear complexes of formulas [Ni₂(L)(L¹)₂N₃]·H₂O (1), [Ni₂(L²)₃(μ_1,1-N₃)]·2H₂O (2), and one tretranuclear complex [Ni₂(L²)₂(NCS)]₂(C₂H₅OH)₂ (3), where L¹ = HOCH₂CH(C₂H₅)NCHC₆H₃(O⁻)(OCH₃) and L² = HO(CH₂)₂NCHC₆H₃(O⁻)(OCH₃). We have characterized these complexes by analytical, crystal structures, and variable temperature magnetic susceptibility measurements. The magnetic properties of the complexes are studied by magnetic susceptibility (χ_M) vs. temperature measurements. The χ_M T vs. T plots reveal that compounds 1, 2 and 3 are ferromagnetically coupled.     

Magnetic Properties of Tetra-Transition-Metal Substituted Weakley-Type Germanotungstates

Magnetic susceptibility investigations have been carried out on a family of the tetra-transition-metal sandwiched Weakley-type germanotungstates Na₁₁H[Co₄(H₂O)₂(α-GeW₉O₃₄)₂]·31H₂O (1), (C₆N₂H₁₈)₄[Co(H₂O)₆]H₂[Co₄(H₂O)₂(α-GeW₉O₃₄)₂]·5.5H₂O (2) and Na(H₂O)₂(C₆N₂H₁₈)_4.75H_1.5[Ni₄(H₂O)₂(α-GeW₉O₃₄)₂]·1.5H₂O (3) with the intention of studying the magnetic exchange properties of the rhomb-like four transition-metal ions in the central belt. The Co–Co and Ni–Ni ferromagnetic exchange interactions are dominant in the rhomb-like M₄O₁₆ units in 1–3. Furthermore, magnetic susceptibility measurements also reveal that the magnetic coupling constant J is a sensitive parameter that is closely realted to the M–O–M angles and M···M separations in the rhomb-like magnetic core. Variable-temperature ac susceptibilities exhibit that magnetic properties of 2 and 3 are related to the spin glassy behaviors.     

Synthesis,characterization and X-ray crystal structures of <Emphasis Type="Italic">N</Emphasis>-2-pyridinyl carbonyl-2-pyridine carboximidate copper(II) complexes

Two copper complexes, [Cu(bpca)(4,4′-bpyH)(H₂O)(ClO₄)]ClO₄·H₂O (1) and [Cu₄(bpca)₄(mpba)]·3H₂O (2) [bpca = N-2-pyridinylcarbonyl-2-pyridine-carboximidate; mpba = 1,3-phenylenebis(oxamate)] were synthesized and characterized by physico-chemical and spectroscopic techniques. Complex 1 crystallizes in the Triclinic P-1 space group while complex 2 is in the Monoclinic space group C2/c. Bpca acts as a tridentate ligand through its three nitrogen atoms in these species. They exhibit 2D supramolecular architectures through hydrogen bonds and short-distance intermolecular interactions. Magnetic measurements in the range 2–300 K have shown weak antiferromagnetic interactions between the adjacent copper ions in complex 2. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Solid Phase Synthesis, Characterization of Hexamethylenetetramine Complexes of Antimony and Bismuth Trichloride

New hexamethylenetetramine complexes of antimony and bismuth trichloride were synthesized through a solid phase reaction of hexamethylenetetramine and antimony or bismuth trichloride. The formula of the complex is MCl₃(C₆H₁₂N₄)₂⋅H₂O (M=Sb, Bi).The crystal structure of the complexes belongs to monoclinic system and the lattice parameters: a=1.249 nm, b=1.4583 nm, c=1.6780 nm andβ=91.78° for SbCl₃(C₆H₁₂N₄)₂⋅H₂O and a=1.3250 nm, b=1.3889 nm, c=1.7449 nm and β=98.94° for BiCl₃(C₆H₁₂N₄)₂⋅H₂O. Far-infrared spectra reveal that the antimony or bismuth ion is coordinated by the nitrogen atom of the hexamethylenetetramine. The thermal analysis also demonstrates the complex formation between the antimony or bismuth ion and hexamethylenetetramine. The intermediate and final residues in the thermal decomposition process have been analyzed to check the pyrolysis reaction. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis, characterization and standard molar enthalpy of formation of Nd(C7H5O3)2·(C9H6NO)

The complex from reaction of neodymium chloride six-hydrate with salicylic acid and 8-hydroxyquinoline, Nd(C₇H₅O₃)₂·(C₉H₆NO), was synthesized and characterized by IR, elemental analysis, molar conductance, and thermogravimatric analysis. The standard molar enthalpies of solution of [NdCl₃·6H₂O(s)], [2C₇H₆O₃(s)], [C₉H₇NO(s)] and [Nd(C₇H₅O₃)₂·(C₉H₆NO)(s)] in a mixed solvent of anhydrous ethanol, dimethyl formamide (DMF) and perchloric acid were determined by calorimetry at 298.15 K. Based on Hess’ law, a new chemical cycle was designed, and the enthalpy change of the reaction

X-ray,Thermal and Infrared Spectroscopic Studies on Potassium,Rubidium and Caesium Uranyl Oxalate Hydrates

M₂UO₂(C₂O₄)₂⋅nH₂O compounds (M=K, Rb and Cs)have been prepared and characterized by chemical and thermal analyses as well as by X-ray diffraction and infrared spectroscopy. X-ray powder data show that the compounds belong to an orthorhombic system. Thermal and infrared studies show that the compounds decompose to M₂UO₄ through the formation of alkali metal carbonate and UO₂ as intermediates. K₂UO₂(C₂O₄)₂⋅3H₂O, and Rb₂UO₂(C₂O₄)₂⋅2H₂O gave K₂UO₄, Rb₂UO₄ at 700 and 600°C respectively, while in the case of Cs₂UO₂(C₂O₄)₂⋅2H₂O, the intermediate products of decomposition reacted to yield Cs₂U₄O₁₃ at 1000°C. This revised version was published online in July 2006 with corrections to the Cover Date.     

杂金属杯[4]配位聚合物的合成与表征

合成了4个杂金属杯[4]配位聚合物{[Cd（L）（tpa）]·3H₂O}_n（1）,{[Zn₂（L）₂（tpa）₂]·3H₂O}_n（2）,{[Co（L）（oba）]·2DMA·0.5H₂O}_n（3）和{[Zn（L）（oba）]·DMA}_n（4）（L=2-（1H-咪唑基-甲基）-6-（3-（1H-咪唑基-甲基）-5-叔丁基-2-羟基）苄基-4-叔丁基苯酚,H₂tpa=对苯二甲酸,H₂oba=4,4''-二苯醚二甲酸）,并通过元素分析、热重、红外光谱、固态紫外、单晶X射线衍射和粉末X射线衍射对其进行了表征。单晶结构分析表明晶体1是单斜晶系,P2₁/n空间群,而晶体2,3和4均为三斜晶系,P1空间群。化合物1,2,3和4是由0维[M（N₄O₂C₂₉H₃₆）]（M=Zn,Co,Cd）的杂金属杯[4]与配体对苯二甲酸和4,4''-二苯醚二甲酸形成的一维配位聚合物。