988 resultados para CU-2
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Tesis (Doctor en IngenierÃa de Materiales) UANL, 2012.
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Tesis (Doctor en IngenierÃa de Materiales) UANL, 2012.
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Tesis (Doctor en Ciencias con Orientación en QuÃmica de los Materiales) UANL, 2013.
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Le présent mémoire décrit la synthèse et l’utilité de complexes Cu-NHC. En premier lieu, la synthèse de complexes de cuivre porteurs de ligand(s) de type carbène-N-hétérocyclique (NHC) via une génération décarboxylative de carbènes sera présentée. En effet, de précédents rapports font état de l’utilisation de carboxylates d’imidazol(in)ium en tant que précurseurs carbéniques sous conditions thermolytiques. Ainsi, la présente étude montre l’utilisation de ces espèces zwitterioniques pour la synthèse de complexes de cuivre(I) mono- et bis-NHC comportant divers substituants et contre-ions. Une seconde partie du projet se concentrera sur l’évaluation de complexes Cu-NHC en tant que catalyseurs pour la synthèse de 2,2’-binaphtols via une réaction de couplage oxydatif de naphtols. L’objectif de ce projet de recherche est d’étudier les effets de variations structurales de différents complexes Cu-NHC afin de construire un processus catalytique plus efficace. Les effets de la structure du catalyseur sur la réaction de couplage ont été évalués en variant son contre-ion, le nombre de ligands NHC se coordonnant au cuivre, ainsi que la nature des substituants du ligand.
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In this regard Schiff base complexes have attracted wide attention. Furthermore, such complexes are found to play important role in analytical chemistry, organic synthesis, metallurgy, refining of metals, electroplating and photography. Many Schiff base complexes are reported in literature. Their properties depend on the nature of the metal ion as well as on the nature of the ligand. By altering the ligands it is possible to obtain desired electronic environment around the metal ion. Thus there is a continuing interest in the synthesis of simple and zeolite encapsulated Schiff base complexes of metal ions. Zeolites have a number of striking structural similarities to the protein portion of natural enzymes. Zeolite based catalysts are known for their remarkable ability of mimicking the chemistry of biological systems. In view of the importance of catalysts in all the areas of modern chemical industries, an effort has been made to synthesize some simple Schiff base complexes, heterogenize them by encapsulating within the supercages of zeoliteY cavities and to study their applications. The thesis deals with studies on the synthesis and characterization of some simple and zeoliteY encapsulated Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) complexes and on the catalytic activity of these complexes on some oxidation reactions. Simple complexes were prepared from the Schiff base ligands SBT derived from 2-aminobenzothiazole and salicylaldehyde and the ligand VBT derived from 2-aminobenzothiazole and vanillin (4-hydroxy-3- methoxybenzaldehyde). ZeoliteY encapsulated Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) complexes of Schiff base ligands SBT and VBT and also of 2-aminobenzothiazole were synthesized. All the prepared complexes were characterized using the physico-chemical techniques such as chemical analysis (employing AAS and CHN analyses), magnetic moment studies, conductance measurements and electronic and FTIR spectra. EPR spectra of the Cu(II) complexes were also carried out to know the probable structures and nature of Cu(II) complexes. Thermogravimetric analyses were carried out to obtain the information regarding the thermal stability of various complexes. The successful encapsulations of the complexes within the cavities of zeoliteY were ascertained by XRD, surface area and pore volume analysis. Assignments of geometries of simple and zeoliteY encapsulated complexes are given in all the cases. Both simple and zeoliteY encapsulated complexes were screened for catalytic activity towards oxidation reactions such as decomposition of hydrogen peroxide, oxidation of benzaldehyde, benzyl alcohol, 1-propanol, 2-propanol and cyclohexanol.
Studies on Some Transition Metal Complexes of Schiff Bases Derived from Quinoxaline-2-carboxaldehyde
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Two series of transition metal complexes of Schiff bases derived from quinoxaline-2-carboxaldehyde with semicarbazide (QSC) and furfurylamine (QFA) were synthesised and characterised by elemental analyses, molar conductance and magnetic susceptibility measurements, IR, electronic and EPR spectral studies. The QSC complexes have the general formula [M(QSC)Cl2]. A tetrahedral structure has been assigned for the Mn(II), Co(II) and Ni(II) complexes and a square-planar structure for the Cu(II) complex. The QFA complexes have the formula [M(QFA)2Cl2]. An octahedral structure has been assigned for these complexes. All of the complexes exhibit catalytic activity towards the oxidation of 3,5-di-tert-butylcatechol (DTBC) to 3,5-di-tert-butylquinone (DTBQ) using atmospheric oxygen. The cobalt(II) complex of the ligand QFA was found to be the most active catalyst.
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Some new transition metal complexes of the Schiff base quinoxaline-2-car boxalidene-2-aminophenol (HQAP) have been synthesized and characterized by elemental analyses, conductance and magnetic measurements and IR and UV-Visible spectral studies. The complexes have the following empirical formulae: [Mn(QAP121, [Fe(QAPl2C1I, [Co(QAPl21, [Ni(QAP121 and [Cu(QAP121. A tetrahedral structure has been assigned for the manganese(=), cobalt(II1, nickel(II1 and copper(II1 complexes. For the iron(IIIl complex an octahedral dimeric structure has been suggested
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Ten copper(II) complexes {[CuL1Cl] (1), [CuL1NO3]2 (2), [CuL1N3]2 · 2/3H2O (3), [CuL1]2(ClO4)2 · 2H2O (4), [CuL2Cl]2 (5), [CuL2N3] (6), [Cu(HL2)SO4]2 · 4H2O (7), [Cu(HL2)2] (ClO4)2 · 1/2EtOH (8), [CuL3Cl]2 (9), [CuL3NCS] · 1/2H2O (10)} of three NNS donor thiosemicarbazone ligands {pyridine-2-carbaldehyde-N(4)-p-methoxyphenyl thiosemicarbazone [HL1], pyridine-2-carbaldehyde-N(4)-2-phenethyl thiosemicarbazone [HL2] and pyridine-2-carbaldehyde N(4)-(methyl), N(4)-(phenyl) thiosemicarbazone [HL3]} were synthesized and physico-chemically characterized. The crystal structure of compound 9 has been determined by X-ray diffraction studies and is found that the dimer consists of two square pyramidal Cu(II) centers linked by two chlorine atoms.
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Spinel systems with the composition of Cu 1−x Zn x Cr 2 O 4 [x = 0 CCr, x = 0.25 CZCr-1, x = 0.5 CZCr-2, x = 0.75 CZCr-3 and x = 1 ZCr] were prepared by homogeneous co-precipitation method and were characterized by X-ray diffraction (XRD) and FT-IR spectroscopy. Elemental analysis was done by EDX, and surface area measurements by the BET method. The redox behavior of these catalysts in cyclohexane oxidation at 243 K using TBHP as oxidant was examined. Cyclohexanone was the major product over all catalysts with some cyclohexanol. 69.2% selectivity to cyclohexanol and cyclohexanone at 23% conversion of cyclohexane was realized over zinc chromite spinels in 10 h.
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Coordination chemistry of pentadentate 2,6-diacetylpyridine bis(thiosemicarbazone) Schiff base ligands has been intensively studied due to the versatility of the molecular chain in order to obtain very different geometries as well as their broad therapeutic activity. Metal complexes of thiosemicarbazone with aldehydes and ketones have been widely reported. But there have been fewer reports on potential pentadentate bis(thiosemicarbazones) formed from 2,6-diacetylpyridine. Keeping these in view, we have synthesized four bis(thiosemicarbazone) systems with 2,6-diacetylpyridine. In the present work, the chelating behavior of bis(thiosemicarbazones) are studied, with the aim of investigating the influence of coordination exerts on their conformation and or configuration, in connection with the nature of the metal and of the counter ion. The selection of the 2,6-diacetylpyridine as the ketonic part was based on its capability to form polynuclear complexes with different coordination number. The doubled armed bis(thiosemicarbazones) can coordinate to a metal centre as dianionic ligand by losing its amide protons or it can coordinate as monoanionic ligand by losing its amide proton from one of the thiosemicarbazone moiety or it can also be coordinate as neutral ligand. Hence it is interesting to explore the coordinating capabilities of these ligands whether in neutral form or anionic form and to study the structural variations occurring in the ligands during complexation such as change in conformation.
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This thesis is mainly concerned with the synthesis and characterisation of new simple and zeolite encapsulated transition metal (manganese(II),nickel(II),and copper(II)complexes of quinoxaline based double Schiff base ligands.Theses ligands are N,N'-bis(quinoxaline-2-carboxalidene)hydrazine,N,N'-bis(quinoxaline-2-carboxalidene)-1,2-diaminoethane,N,N'-bis(quinoxaline-2-carboxalidene)-1,3-diamonopropane,N,N'-bis(quinoxaline-2-carboxalidene)-1,4-diaminobutane,N,N'-bis(quinoxaline-2-carboxalidene)-1,2-diaminocyclohexane and N,N'-bis(quinoxaline-2-carboxalidene)-1,2-diaminobenzene.The Schiff base ligands have been characterised by spectral and single crystal XRD studies.Theses ligands provide great structural diversity during complexation.Mn(II) and Ni(II) form octahedral with these Schiff bases,whereas Cu(II) forms both octahedral and tetrahedral complexes.Studies on the biological and Catalytic activity of the copper(ll) complexes are also presented in this thesis.
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This thesis deals with the synthesis, characterisation and catalytic activity studies of some new transition metal complexes of the Schiff bases, derived from quinoxaline—2—carboxaldehyde. The model complexes derived from specially designed and synthesised Schiff bases help us to understand the chemistry of biological systems. Schiff bases derived from heterocyclic aldehydes like quinoxaline-2-carboxaldehyde provide great structural diversity during complexation. The Schiff bases synthesised in the present study ' are quinoxaline—2—carboxa.lidene-2-aminophenol (QAP). quinoxaline—2carboxaldehyde semicarbazone (QSC), quinoxaline-2—carboxalidene—o— phenylenediamine (QOD) and quinoxaline-2-carboxalidene-2-furfurylamine (QFA). The elucidation of the structure of these complexes is done using conductance, magnetic susceptibility measurements. infrared, UV—Vis and EPR spectral studies.
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The work embodied in the thesis is divided into eight chapters. Chapter I gives a brief introduction about metal complexes of thiosemicarbazones, including their structural and bonding properties. Chapter 2 deals with the synthesis and single crystal X-ray diffraction studies of various thiosemicarbazones used up for the present investigations and various characterization techniques. Chapter 3 deals with synthesis, spectral and structural studies of Cu(U) complexes with ONS donor thiosemicarbazones. Chapter 4 deals with synthesis and spectral studies of Ni(II) complexes \vith 2-hydroxyacetophenone N(4)-cyclohexyl thiosemicarbazone as the ligand. Chapter 5 includes synthesis and spectral studies of Mn(II) complexes. Chapter 6 deals with synthesis, spectral and structural studies of Zn(II) complexes. Chapter 7 includes synthesis and spectral studies of oxovanadium(IV) complexes. Chapter 8 deals with synthesis, spectral and single crystal X-ray diffraction studies of dioxomolybdenum(VI) complexes.
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An interesting series of nine new copper(II) complexes [Cu2L2(OAc)2] H2O (1), [CuLNCS] ½H2O (2), [CuLNO3] ½H2O (3), [Cu(HL)Cl2] H2O (4), [Cu2(HL)2(SO4)2] 4H2O (5), [CuLClO4] ½H2O (6), [CuLBr] 2H2O (7), [CuL2] H2O (8) and [CuLN3] CH3OH (9) of 2-benzoylpyridine-N(4)-phenyl semicarbazone (HL) have been synthesized and physico-chemically characterized. The tridentate character of the semicarbazone is inferred from IR spectra. Based on the EPR studies, spin Hamiltonian and bonding parameters have been calculated. The g values, calculated for all the complexes in frozen DMF, indicate the presence of the unpaired electron in the dx2 y2 orbital. The structure of the compound, [Cu2L2(OAc)2] (1a) has been resolved using single crystal X-ray diffraction studies. The crystal structure revealed monoclinic space group P21/n. The coordination geometry about the copper(II) in 1a is distorted square pyramidal with one pyridine nitrogen atom, the imino nitrogen, enolate oxygen and acetate oxygen in the basal plane, an acetate oxygen form adjacent moiety occupies the apical position, serving as a bridge to form a centrosymmetric dimeric structure
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Desarrollar el concepto de Educaci??n Ambiental que se refleja en el proyecto Anida, y que consiste en un proceso educativo global que trata de capacitar al educando para: estudiar cient??fica e interdisciplinarmente el medio ambiente; desarrollar una actitud responsable ante la utilizaci??n de los recursos naturales; analizar cr??ticamente la gesti??n del medio en sus distintas escalas: local, regional, nacional y planetaria participar de forma activa en la b??squeda de soluciones - apreciar los valores de un medio ambiente libre, equilibrado, sano y enriquecedor en sus tres facetas: natural, social y cultural. El objeto del trabajo es desarrollar un ??rea natural constitu??da por el Macizo calc??reo de Pe??a Cabarga y en ella desarrollar una serie de itinerarios did??ctico-ambientales como el que se expone en este trabajo. El trabajo va desarrollando las paradas a realizar dentro de este itinerario, 2: el eucaliptal, los elementos del paisaje, la ladera caliza carstificada, los prados de siega y el encinar c??ntabro. Analizando en cada una de ellas las variables: flora, fauna, paisaje, rocas, tierra, actividades humanas sobre el medio ambiente, infraestructura, etc.. La informaci??n se ha obtenido realizando un estudio del ??rea natural de Pe??a Cabarga, y a trav??s de un seminario permanente de Educaci??n Ambiental de Cantabria, en el que se aportaban las experiencias y los problemas surgidos a cada profesor. Se analiza conceptualmente cada uno de los aspectos m??s importantes a tener en cuenta en cada una de las paradas del itinerario. El resultado es este cuadernillo dirigido al profesor en el que se va desarrollando todo el itinerario, analizando desde el principio las actividades que ha de desarrollar el profesor para conseguir los objetivos, el material que ha de utilizar, cu??les son las especies que se va a encontrar y c??mo tratarlas, c??mo organizar la clase para la realizaci??n del itinerario, los aspectos m??s importantes a destacar en cada una de las paradas. La pr??ctica de las t??cnicas y metodolog??as adecuadas para el estudio del medio va a dotar al alumno de los conocimientos cient??ficos sobre el mismo, pero adem??s va a desarrollar su capacidad de an??lisis cr??tico de la gesti??n ambiental.