Reação de bis-inserção de 1,2-difenilacetileno na ligação Pd-C de ciclometalados

The present paper deals with the bis-insertion reactions of 1,2-diphenylacetylene into Pd-C bond of the cyclopalladated complexes [Pd(dmba)(µ-NCO)]2 (1) and [Pd(dmba)(MeCN)2](NO3) (2) (dmba = N,N-dimethylbenzylamine, MeCN = acetonitrile). Two new complexes [Pd{PhC=CPh-CPh=CPhC6H4CH2N(CH 3)2}(NCO)] (3) and [Pd{PhC=CPh-CPh=CPhC6H4CH2N(CH 3)2}(NO3 )] (4) were obtained and characterized by IR and NMR spectroscopy and elemental analysis.

Novel neutral iron(II) isocyanide maleonitrile dithiolate [Fe(S2C2(CN)2)(t-BuNC) 4] compound

FeBr2 reacts with the S2C2(CN)2(2-) ion (1:1 ratio) in the presence of an excess of t-BuNC in THF to give the mixed ligand [Fe(S2C2(CN)2)(t-BuNC) 4] compound. This neutral product with a formal oxidation state of two for the iron atom was characterized by conductivity measurements, and, i.r., Mössbauer, 13C and ¹H n.m.r. spectroscopy. There is a Fe-C pi back-donation strengthened towards isocyanide ligands, according to the data of 13C, ¹H n.m.r. and Mössbauer spectroscopy.

Utilização de um eletrodo de grafite-epóxi recoberto com [Zn(FEN)3][tetratris(4-clorofenil) borato]2 sensível a zinco(II) em meio 1,10-fenantrolina como eletrodo indicador em titulações potenciométricas de precipitação

The construction and analytical evaluation of a coated graphite-epoxy electrode sensitive to the zinc-1,10-phenantroline complex based on the [Zn(fen)3][tetrakis(4-chlorophenyl)borate]2 incorporated into a poly(vinylchloride) (PVC) matrix are described. A thin membrane film of this ion-pair, dibutylphthalate (DBPh) and PVC were deposited directly onto an electrically conductive graphite-epoxy support located inside a Perspex® tube. The best PVC polymeric membrane contains 65% (m/m) DBPh, 30% (m/m) PVC and 5% (m/m) of the ion-pair. This electrode shows a response of 19.5 mV dec-1 over the zinc(II) concentration range of 1.0 x 10-5 to 1.0 x 10-3 mol L-1 in 1,10-phenantroline medium, at pH 6.0. The response time was less than 20 seconds and the lifetime of this electrode was more than four months (over 1200 determinations by each polymeric membrane). It was successfully used as an indicator electrode in the potentiometric precipitation titration of zinc(II) ions.

Determinação espectrofotométrica indireta de capsaicinoides em pimentas Capsicum a partir da reação com o complexo de Co(II) com 4-(2-piridilazo) resorcinol

Capsaicinoids (CAPS) are substances responsible for pungency in Capsicum. It is important to quantify these types of compounds owing to their broad application in food, pharmaceuticals, cosmetics and chemical weapons. In this work, we developed an indirect spectrophotometric method based on the colorimetric reaction between CAPS, Co(II) 3.10×10-5 mol L-1 and 4-(2-pyridylazo) resorcinol (PAR) 6.23×10-5 and, in cachaça:water 92:8v/v solutions, for quantification of total CAPS in Capsicum peppers. The product of the reaction is CoPAR2CAPS2 and its absorption in aquo-ethanolic solution at 510 nm is proportional to the total CAPS concentration from 0.60 to 17.94 mg L-1. The values of limit of detection and limit of quantification were 0.0004 and 0.001 mg of CAPS/g of pepper, respectively, with 4% relative standard deviation. The developed method yielded similar results to those obtained from high performance liquid chromatography, with 95% of confidence.

Potentiometric determination of Nickel (II) ion using 2-hydroxy-1-naphthylidene-N-cyanoacetohydrazone as electroactive material

A potentiometric Nickel sensor was prepared using 2-hydroxy-1-naphthylidene-N-cyanoacetohydrazone as electro-active material and epoxy resin as a binding material. A membrane composed of 40% Schiff's base and 60% epoxy resin exhibited the best performance. The membrane showed excellent response in the concentration range of 0.15 ppm to 0.1 mol L- 1 Ni+2 ions with non-Nernstian slope of 22.0 mV/decade, had a rapid response time (less than 10 s), and can be used for three months without any considerable loss of potential. The sensor was useful within the pH range of 1.3 to 9.6, and was able to discriminate between Ni2+ and a large number of alkaline earth and transition metal ions. The practical utility of the sensor has been demonstrated by using it successfully as an indicator electrode in the potentiometric titration of Ni2+ with EDTA and oxalic acid.

Ni(II), Cu(II), AND Zn(II) COMPLEXES DERIVED FROM A NEW SCHIFF BASE 2-((Z)-(3-METHYLPYRIDIN-2- YLEIMINO)METHYL)PHENOL AND SYNTHESIS OF NANO SIZED METAL OXIDE PARTICLES FROM THESE COMPOUNDS

Synthesis, spectral identification, and magnetic properties of three complexes of Ni(II), Cu(II), and Zn(II) are described. All three compounds have the general formula [M(L)2(H2O)2], where L = deprotonated phenol in the Schiff base 2-((z)-(3-methylpyridin-2-yleimino)methyl)phenol. The three complexes were synthesized in a one-step synthesis and characterized by elemental analysis, Fourier transform infrared spectroscopy, electronic spectra, X-ray diffraction (XRD), and room temperature magnetic moments. The Cu(II) and Ni(II) complexes exhibited room temperature magnetic moments of 1.85 B.M. per copper atom and 2.96 B.M. per nickel atom. The X-band electron spin resonance spectra of a Cu(II) sample in dimethylformamide frozen at 77 K (liquid nitrogen temperature) showed a typical ΔMS = ± 1 transition. The complexes ([M(L)2(H2O)2]) were investigated by the cyclic voltammetry technique, which provided information regarding the electrochemical mechanism of redox behavior of the compounds. Thermal decomposition of the complexes at 750 ºC resulted in the formation of metal oxide nanoparticles. XRD analyses indicated that the nanoparticles had a high degree of crystallinity. The average sizes of the nanoparticles were found to be approximately 54.3, 30.1, and 44.4 nm for NiO, CuO, and ZnO, respectively.

Clivagem dos ciclopaladados diméricos [Pd(dmba)(m-X)]2 (dmba = N,N-dimetilbenzilamina; X = Cl, N3, NCO) por tiouréia

Ciclopaladados diméricos do tipo [Pd(dmba)(m-X)]2 (dmba = N,N-dimetilbenzilamina; X = Cl, N3, NCO) reagem com tiouréia (tu), à temperatura ambiente, resultando espécies mononucleares do tipo [Pd(dmba)(X)(tu)]. Todos os compostos foram caracterizados por análise elementar, espectroscopias no IV e de RMN de ¹H e com base nessas técnicas as estruturas, desses compostos, foram propostas. Os espectros de absorção no infravermelho mostraram que a coordenação da tiouréia, ao paládio, ocorre através do átomo de enxofre. O anel ciclometalado foi confirmado através da espectroscopia de RMN de ¹H.

Magnetic, thermal and spectral characterization of 2,6-dimethoxybenzoates of Co(II), Ni(II) and Cu(II)

The complexes of 2,6-dimethoxybenzoic acid anion with ions of Co(II), Ni(II), and Cu(II) have been synthesized as polycrystalline solids, and characterized by elemental analysis, spectroscopy, magnetic studies, and also by X-ray diffraction and thermogravimetric measurements. The analysed complexes have following colours: pink for Co(II), green for Ni(II), and blue for Cu(II) compounds. The carboxylate group binds as monodentate, and bidentate bridging and chelating ligands. On heating in air to 1173 K the complexes decompose in four, three or two steps. At first, they dehydrate in one or two steps to anhydrous salts, that next decompose to oxides of the respective metals. The solubility of the investigated dimethoxybenzoates in water at 293 K is of the order of 10-2 mol/dm3. Their magnetic moments were determined in the temperature range of 76-303 K. The results reveal the compounds of Co(II) and Ni(II) to be high-spin complexes and that of Cu(II) to form dimer.

Magnetic, thermal and spectral behaviour of 3-chloro-2-nitrobenzoates of Co(II), Ni(II), and Cu(II)

Physico-chemical properties of 3-chloro-2-nitrobenzoates of Co(II), Ni(II) and Cu(II) were synthesized and studied. The complexes were obtained as mono- and dihydrates with a metal ion to ligand ratio of 1 : 2. All analysed 3-chloro-2-nitrobenzoates are polycrystalline compounds with colours depending on the central ions: pink for Co(II), green for Ni(II) and blue for Cu(II) complexes. Their thermal decomposition was studied in the range of 293 ­ 523 K, because it was found that on heating in air above 523 K 3-chloro-2-nitrobenzoates decompose explosively. Hydrated complexes lose crystallization water molecules in one step and anhydrous compounds are formed. The final products of their decomposition are the oxides of the respective transition metals. From the results it appears that during dehydration process no transformation of nitro group to nitrite takes place. The solubilities of analysed complexes in water at 293 K are of the order of 10-4 ­ 10-2 mol / dm³. The magnetic moment values of Co2+, Ni2+ and Cu2+ ions in 3-chloro-2-nitrobenzoates experimentally determined at 76 ­ 303 K change from 3.67µB to 4.61µB for Co(II) complex, from 2.15µB to 2.87µB for Ni(II) 3-chloro-2-nitrobenzoate and from 0.26µB to 1.39µB for Cu(II) complex. 3-Chloro-2-nitrobenzoates of Co(II) and Ni(II) follow the Curie-Weiss law. Complex of Cu(II) forms dimer.

Crystal structures of 5-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II) and Zn(II)

The crystal and molecular structures of [bis(5-chloro-2-methoxybenzoate)tetraaquamanganese(II)], [pentaaqua(5-chloro-2-methoxybenzoato)cobalt(II)] (5-chloro-2-methoxybenzoate), [pentaaqua(5-chloro-2-methoxybenzoato)nickel(II)] (5-chloro-2-methoxybenzoate) and [aquabis(5-chloro-2-methoxybenzoate)zinc(II)] monohydrate were determined by a single-crystal X-ray analysis. Mn(H2O)4L2 (where L = C8H6ClO3) crystallizes in the monoclinic system, space group P21/c. [Co(H2O)5L]L and [Ni(H2O)5L]L both are isostructural, space group P212121. The crystals of [Zn(H2O)L2] H2O are monoclinic, space group Pc. Mn(II) ion is positioned at the crystallographic symmetry center. Mn(II) and Co(II) ions adopt the distorted octahedral coordination but Zn(II) tetrahedral one.The carboxylate groups in the complexes with M(II) cations function as monodentate, bidentate and/or free COO-groups. The ligands exist in the crystals as aquaanions. The complexes of 5-chloro-2-methoxybenzoates with Mn(II), Co(II) and Zn(II) form bilayer structure.

Magnetic, thermal and spectral characterization of 2,4-dimethoxybenzoates of Mn(II), Co(II) and Cu(II)

2,4 - Dimethoxybenzoates of Mn(II), Co(II) and Cu(II) have been synthesized as hydrated or anyhydrous polycrystalline solids and characterized by elemental analysis, IR spectroscopy, magnetic studies and X-ray diffraction measurements. They possess the following colours: Mn(II) - white, Co(II) - pink and Cu(II) - blue. The carboxylate groups bind as monodentate, or a symmetrical bidentate bridging ligands and tridentate. The thermal stabilities were determined in air at 293-1173K. When heated the hydrated complexes dehydrate to from anhydous salts which are decomposed to the oxides of respective metals. The magnetic susceptibilites of the 2,4-dimethoxybenzoates were measured over the range 76-303 K and their magnetic moments were calculated. The results reveal the complexes of Mn(II), Co(II) to be high-spin complexes and that of Cu(II) to form dimer.

Melody II, Op. 17 N:o 2

Ei vapaa, vapautuu 2027. Kosti Vehanen (1887-1957).

Comparison of some properties of 2,3 - and 3,4 - dimethoxybenzoates of Cu(II), Co(II) and Nd(III)

The physicochemical properties of 2,4-, and 3,4- dimethoxybenzoates of Cu(II), Co(II) and Nd(III) were studied and compared to observe the -OCH3 substituent positions in benzene ring on the character of complexes. The analysed compounds are crystalline hydrated or anhydrous salts with colours depending on the kind of central ions: blue for Cu(II), pink for Co(II) and violet for Nd(III) complexes. The carboxylate groups bind as monodentate, bidentate bridging or chelating and even tridentate ligands. Their thermal stabilities were studied in air at 293-1173K. When heated the hydrated complexes release the water molecules and form anhydrous compounds which are then decomposed to the oxides of respective metals. Their magnetic moment values were determined in the range of 76-303K. The results reveal the compounds of Nd(III) and Co(II) to be the high-spin and that of Cu(II) forms dimer. The various positions of -OCH3 groups in benzene ring influence some of physicochemical properties of analysed compounds.

Electrochemical properties of Cu4[PhN3C6H4N3(H)Ph]4(µ-O)2, a tetranuclear Copper(II) complex with 1-phenyltriazenido-2-phenyltriazene-benzene as ligand

Bis-(µ2-oxo)-tetrakis{[1-feniltriazene-1,3-diil)-2-(phenyltriazenil)benzene copper(II) is a tetranuclear complex which shows four Cu(II) ions coordinated by four 1,2-bis(phenyltriazene)benzene bridged ligands, with one diazoaminic deprotonated chain, and two O2- ligands. The complex reduces at E1/2 = -0.95 V vs Fc+/Fc, a two electrons process. Cyclic voltammetric and spectroelectrochemical studies showed a reversible process. When immobilized on carbon paste electrode, the complex electrocatalyses the reduction of O2 dissolved on aqueous solution at -0.3 V vs SCE potential. The obtained current shows linearity with O2 concentration.

The physico-chemical properties of 2-methoxyphenoxyacetates of Mn(II), Co(II), Ni(II) and Cu(II)

The complexes of 2-methoxyhenoxyacetates of Mn(II), Co(II), Ni(II) and Cu(II)with the general formula: M(C9H9O4)3·4H2O, where M(II) = Mn, Co, Ni and Cu have been synthesized and characterized by elemental analysis, IR spectroscopy, magnetic and thermogravimetric studies and also X-ray diffraction measurements. The complexes have colours typical for M(II) ions (Mn(II) - a pale pink, Co(II) - pink, Ni(II) - green, and Cu(II) - blue). The carboxylate group binds as monodentate and bidentate ligands. On heating to 1273K in air the complexes decompose in the same way. At first, they dehydrate in one step to anhydrous salts, that next decompose to the oxides of respective metals with the intermediate formation of the oxycarbonates. Their solubility in water at 293K is of the order of 10-5 mol·dm-3. The magnetic moments of analysed complexes were determined in the range of 76-303K. The results reveal them to be high-spin complexes of weak ligand fields.