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POLYMORPHISM OF FOUR ENANTIOTROPIC CRYSTALLINE SYSTEMS CONTAINING Ni(II), H<sub>2</sub>O, 15-Crown-5 AND NO<sub>3</sub><sup>-</sup>Siegler, Maxime Andre 01 January 2007 (has links)
The series of compounds [M(H2O)2(15-crown-5)](NO3)2, M = Mg, Mn, Co, Cu and Zn, has been extended to include two new phases for M = Fe and two new phases for M = Ni. The system [M(H2O)2(15-crown-5)](NO3)2 is remarkable for having many high-Z’ phases (Z’ > 1) with similar packing and for having solid-solid phase transitions through which there is no significant loss of crystallinity. The synthesis of the analogous Ni complex was carried out. Single-crystal X-ray diffraction showed that the coordination of the Ni2+ ion is different from that of the other six M2+ ions in the system [M(H2O)2(15-crown- 5)](NO3)2.
High temperature phases with high Z’ (8) were isolated for M = Mg, Fe and Zn. The refinements of such phases are challenging because of the lack of information in the diffraction patterns. Full details of the refinements for these three phases are discussed.
Six other Ni(II) complexes consisting of Ni2+, NO3-, 15-crown-5 and different solvents were found when efforts were made to synthesize the compound [Ni(H2O)2(15-crown- 5)](NO3)2. In these chemically different environments, the Ni2+ ions are not coordinated by the 15-crown-5 molecules; rather, one-dimensional H-bonded chains are formed from uncomplexed 15-crown-5 molecules and the Ni(II) complexes.
Among these six Ni(II) complexes, the compounds [Ni(H2O)6](NO3)2·(15-crown-5)·H2O, [Ni(H2O)6](NO3)2·(15-crown-5)·2H2O and [Ni(H2O)2(MeCN)(NO3)2]·(15-crown- 5)·MeCN were found to have reversible solid-solid phase transitions between structurally related phases. In all of these transitions, no significant crystal damage was detectable. The two latter systems are unusual because their phase sequences include three transitions and four phases between 90 and 295 K and because of the existence of high-Z’ phases. These high-Z’ phases are best depicted as being intermediate to low- and hightemperature phases. A method based on thermal analyses and X-ray diffraction has been developed for studying such sets of phase transitions.
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[en] STUDY OF THE NI (II) COMPLEXES WITH THE LIGANDS DODECANETHIOL AND HEXANOIC ACID / [pt] ESTUDO DE COMPLEXOS DE NI (II) COM OS LIGANTES DODECANOTIOL E ÁCIDO HEXANÓICOSERGIO FERNANDES CLARO 15 June 2005 (has links)
[pt] A presença de íons metálicos no petróleo pode afetar a
qualidade dos
produtos da destilação. Com a finalidade de avaliar alguns
efeitos da presença de
Ni (II) no petróleo, realizou-se um estudo de complexos
deste íon com os ligantes
modelo dodecanotiol (que representa o conjunto de
Mercaptanas do petróleo) e o
ácido hexanóico (que representa o conjunto de ácidos
carboxílicos do petróleo). Esse
estudo evidenciou que o Ni (II) pode estar complexado com
outros ligantes do petróleo,
além da porfirina. O complexo de Ni (II) com dodecanotiol
formado no estado sólido, foi
caracterizado pelas técnicas de Espectrometria de Absorção
Atômica (AA),
Espectroscopia de Infravermelho (IV) e Espectroscopia de
Ultravioleta - Visível (UV) ,
Análise Elementar (CHNS-O), e Análise Termogravimétrica
(TGA). Através da
interpretação dos resultados das análises citadas,
concluímos que o complexo sólido
formado, de cor marrom avermelhada, apresenta fórmula
NiC48H102S4 , com hibridação
dsp2 e geometria planar quadrada . O complexo de Ni (II)
com ácido hexanóico foi
formado inicialmente em solução, com a coloração verde, e
após 8 meses, houve a
formação de cristais verdes. Este complexo, foi analisado
pelas técnicas
espectroscópicas de, Ultravioleta-Visível (UV),
Infravermelho (IV), Absorção Atômica
(AA), Análise Termogravimétrica (TGA) e Análise Elementar
(CHNS-O). Com a
interpretação dos resultados das análises realizadas ,
propusemos para o complexo, a
fórmula molecular NiC12H30O8 com hibridação d2sp3 e
geometria octaédrica. / [en] The presence of metal ions in oil can affect the quality
of the distillation products.
With the purpose of evaluating some effects of the
presence of Ni (II) in oil, a study of
complexes of this ion with the model ligands dodecanethiol
(which represents the
mercaptans in oil) and hexanoic acid (which represents the
carboxylic acids in oil) was
performed. This study evidenced that Ni (II) can be
complexed with other ligands present
in oil besides the porphyrins. The complex of Ni (II) with
dodecanethiol was formed in the
solid state, characterized by Atomic Absorption
Spectrometry (AA), Ultraviolet - Visible
Spectroscopy (UV) and Infrared Spectroscopy (IV),
Elemental Analysis (CHNS-O), and
Termogravimetric Analysis (TGA). From the obtained results
it was possible to conclude
that the solid formed, with a reddish - brown color, has
the formula NiC48H102S4, with
dsp2 hybridization and a square planar geometry. The
complex of Ni (II) with hexanoic
acid, was firstly formed in solution having a green color,
and after 8 months green
crystals were formed. This complex was analyzed by Atomic
Absorption (AA), Ultraviolet
- Visible (UV) and Infrared (IV) Spectroscopies,
Termogravimetric Analysis(TGA) and
Elemental Analyze (CHNS-O). It was possible to conclude
that the complex has the
formula NiC12H30O8, with d2sp3 hybridization and an
octahedral geometry .
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[en] SYNTHESIS AND CHARACTERIZATION OF COMPLEXES INVOLVING POLYAMINES AND THE METAL IONS ZINC (II), NICKEL (II) AND PALLADIUM (II) / [pt] SÍNTESE E CARACTERIZAÇÃO DE COMPLEXOS ENVOLVENDO POLIAMINAS E OS ÍONS METÁLICOS ZINCO (II), NÍQUEL (II) E PALÁDIO (II)MARIA STELLA NUNES DE OLIVEIRA 08 October 2010 (has links)
[pt] O presente trabalho descreve a síntese e a caracterização de treze
complexos envolvendo as poliamina etilenodiamina, diaminopropano,
diaminobutano, espermidina e espermina e os íons metálicos Zn (II), Ni (II) e Pd
(II). Todas as sínteses foram realizadas em água, um solvente de importância
biológica, e em condições próximas às fisiológicas, com o objetivo de mimetizar
as ligações e compreender como ocorre a interação das poliaminas com ânions no
ciclo biológico, haja vista que em pH fisiológico essas moléculas se encontram
primordialmente na forma protonada e interagem com biomoléculas aniônicas,
entre essas, determinados sítios do DNA. Utilizou-se para a caracterização dos
complexos as técnicas de condutivimetria, análise elementar, espectrometria de
absorção atômica, análise termogravimétrica, espectroscopia no infravermelho,
espectroscopia de ressonância magnética nuclear de Hidrogênio e Carbono 13
(para os complexos de zinco), difratometria de Raio-X (para os cristais de zinco),
entre outras. Inicialmente foram sintetizados os complexos do tipo
(poliamina[ZnCl(4)]) e, posteriormente, compostos análogos de íon níquel (II) de
estequiometria (poliamina[NiCl(4)]). Observou-se que nesses complexos, as
poliaminas interagem com o ânion tetraclorometalato (II) através de ligações de
hidrogênio. Essas interações ocorrem entre o hidrogênio da amina primária e o
cloro da esfera de coordenação. Os complexos formados pelo íon metálico paládio
(II) apresentaram, conforme as análises realizadas, estruturas químicas distintas
dos demais compostos. Neste caso, foram obtidos os complexos
[Pd(Cl)(2)(C(2)H(8)N(2))], [Pd(Cl)(2)(C(3)H(10)N(2))] e [Pd(2)(Cl)(4)(C(10)H(27)N(4))], que apresentam
importância como possíveis fármacos para o tratamento do câncer. / [en] This paper describes the synthesis and characterization of thirteen
complexes involving the polyamines ethylenediamine, diaminopropane,
diaminobutane, spermidine and spermine, and the metal ions Zn (II), Ni (II) and
Pd (II). All syntheses were performed in water, a solvent of biological importance,
and under near-physiological changes in order to mimic the bonds and understand
the interaction of polyamines with anions in the biological cycle. At physiological
pH these molecules are primarily in the protonated form and interact with anionic
molecules, among which certain DNA sites. The complexes were characterized by
the techniques of conductivity, elemental analysis, atomic absorption
spectrometry, thermogravimetric analysis, infrared spectroscopy, nuclear
magnetic resonance of Hydrogen and Carbon 13 (for the zinc complexes), and Xray
diffraction (for zinc crystals). The complexes of the type (polyamine [ZnCl4])
were synthesized first and, subsequently, analogous compounds of ion nickel (II)
with stoichiometry (polyamine [NiCl4]) were synthesized. It was observed that in
these complexes, the polyamines interact with the tetrachlorometalate (II) anion
via hydrogen bonds. These interactions occur between the primary amine
hydrogen and the chlorine from the coordination sphere. The metal ion complexes
formed by palladium (II) showed, as the analysis data, chemical structures distinct
from the other compounds. In this case, we obtained the complex
[Pd(Cl)(2)(C(2)H(8)N(2))], [Pd(Cl)(2)(C(3)H(10)N(2))] e [Pd(2)(Cl)(4)(C(10)H(27)N(4))], which have
importance as potential drugs for the treatment of cancer.
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An interplay between the spin density distribution and magnetic superexchange interactions: a case study of mononuclear [nBu4N]2[Cu(opooMe)] and novel asymmetric trinuclear [Cu3(opooMe)(pmdta)2](NO3)2·3MeCNAbdulmalic, Mohammad A., Aliabadi, Azar, Petr, Andreas, Krupskaya, Yulia, Kataev, Vladislav, Büchner, Bernd, Hahn, Torsten, Kortus, Jens, Rüffer, Tobias 08 April 2014 (has links) (PDF)
Treatment of the diethyl ester of o-phenylenebis(oxamic acid) (opbaH2Et2, 1) with 5/6 equivalent of MeNH2 in abs. EtOH results in the exclusive formation of the ethyl ester of o-phenylene(N′-methyl oxamide)(oxamic acid) (opooH3EtMe, 2) in ca. 50% yield. Treatment of 2 with four equivalents of [Me4N]OH followed by the addition of Cu(ClO4)2·6H2O gave [Me4N]2[Cu(opooMe)]·H2O (3A) in ca. 80% yield. As 3A appears to be a hygroscopic solid, the related [nBu4N]+ salts [nBu4N]2[M(opooMe)]·H2O (M = Cu (3B), Ni (4)) have been synthesized. By addition of two equivalents of [Cu(pmdta)(NO3)2] to a MeCN solution of 3B the novel asymmetric trinuclear complex [Cu3(opooMe)(pmdta)2](NO3)2 (5) could be obtained in ca. 90% yield. Compounds 2, 3A, 3B, 4 and 5 have been characterized by elemental analysis and NMR/IR spectroscopy. Furthermore, the solid state structures of 3A in the form of [Me4N]2[Cu(opooMe)]·MeOH (3A′), 3B in the form of [nBu4N]2[Cu(opooMe)] (3B′), 4 in the form of [nBu4N]2[Ni(opooMe)]·1.25H2O (4′) and 5 in the form of [Cu3(opooMe)(pmdta)2] (NO3)2·3MeCN (5′), respectively, have been determined by single-crystal X-ray diffraction studies. By controlled cocrystallization, diamagnetically diluted 3B (1%) in the host lattice of 4 (99%) in the form of single crystals have been made available, allowing single crystal EPR studies to extract all components of the g-factor and the tensors of onsite CuA and transferred NA hyperfine interaction. Out of these studies the spin density distribution of the [Cu(opooMe)]2− complex fragment could be determined. The magnetic properties of 5 were studied by susceptibility measurements versus temperature. An intramolecular J parameter of −65 cm−1 has been obtained, unexpectedly, as 5 should possess two different J values due to its two different spacers between the adjacent CuII ions, namely an oxamate (C2NO3) and an oxamidate (C2N2O2) fragment. This unexpected result is explained by a summarizing discussion of the experimentally obtained EPR results (spin density distribution) of 3B, the geometries of the terminal [Cu(pmdta)]2+ fragments of 5 determined by X-ray crystallographic studies and accompanying quantum chemical calculations of the spin density distribution of the mononuclear [Cu(opooMe)]2− and of the magnetic exchange interactions of trinuclear [Cu3(opooMe)(pmdta)2]2+ complex fragments. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.
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An interplay between the spin density distribution and magnetic superexchange interactions: a case study of mononuclear [nBu4N]2[Cu(opooMe)] and novel asymmetric trinuclear [Cu3(opooMe)(pmdta)2](NO3)2·3MeCNAbdulmalic, Mohammad A., Aliabadi, Azar, Petr, Andreas, Krupskaya, Yulia, Kataev, Vladislav, Büchner, Bernd, Hahn, Torsten, Kortus, Jens, Rüffer, Tobias January 2012 (has links)
Treatment of the diethyl ester of o-phenylenebis(oxamic acid) (opbaH2Et2, 1) with 5/6 equivalent of MeNH2 in abs. EtOH results in the exclusive formation of the ethyl ester of o-phenylene(N′-methyl oxamide)(oxamic acid) (opooH3EtMe, 2) in ca. 50% yield. Treatment of 2 with four equivalents of [Me4N]OH followed by the addition of Cu(ClO4)2·6H2O gave [Me4N]2[Cu(opooMe)]·H2O (3A) in ca. 80% yield. As 3A appears to be a hygroscopic solid, the related [nBu4N]+ salts [nBu4N]2[M(opooMe)]·H2O (M = Cu (3B), Ni (4)) have been synthesized. By addition of two equivalents of [Cu(pmdta)(NO3)2] to a MeCN solution of 3B the novel asymmetric trinuclear complex [Cu3(opooMe)(pmdta)2](NO3)2 (5) could be obtained in ca. 90% yield. Compounds 2, 3A, 3B, 4 and 5 have been characterized by elemental analysis and NMR/IR spectroscopy. Furthermore, the solid state structures of 3A in the form of [Me4N]2[Cu(opooMe)]·MeOH (3A′), 3B in the form of [nBu4N]2[Cu(opooMe)] (3B′), 4 in the form of [nBu4N]2[Ni(opooMe)]·1.25H2O (4′) and 5 in the form of [Cu3(opooMe)(pmdta)2] (NO3)2·3MeCN (5′), respectively, have been determined by single-crystal X-ray diffraction studies. By controlled cocrystallization, diamagnetically diluted 3B (1%) in the host lattice of 4 (99%) in the form of single crystals have been made available, allowing single crystal EPR studies to extract all components of the g-factor and the tensors of onsite CuA and transferred NA hyperfine interaction. Out of these studies the spin density distribution of the [Cu(opooMe)]2− complex fragment could be determined. The magnetic properties of 5 were studied by susceptibility measurements versus temperature. An intramolecular J parameter of −65 cm−1 has been obtained, unexpectedly, as 5 should possess two different J values due to its two different spacers between the adjacent CuII ions, namely an oxamate (C2NO3) and an oxamidate (C2N2O2) fragment. This unexpected result is explained by a summarizing discussion of the experimentally obtained EPR results (spin density distribution) of 3B, the geometries of the terminal [Cu(pmdta)]2+ fragments of 5 determined by X-ray crystallographic studies and accompanying quantum chemical calculations of the spin density distribution of the mononuclear [Cu(opooMe)]2− and of the magnetic exchange interactions of trinuclear [Cu3(opooMe)(pmdta)2]2+ complex fragments. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.
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