Detalles MARC
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06440nam a2200361 a 4500 |
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ELB85617 |
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FlNmELB |
| 006 - FIXED-LENGTH DATA ELEMENTS--ADDITIONAL MATERIAL CHARACTERISTICS |
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m o d | |
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cr cn||||||||| |
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201208r2011 ag |||||s|||||||||||spa d |
| 035 ## - SYSTEM CONTROL NUMBER |
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(MiAaPQ)EBC3200667 |
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| System control number |
(Au-PeEL)EBL3200667 |
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| System control number |
(CaPaEBR)ebr10577239 |
| 035 ## - SYSTEM CONTROL NUMBER |
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| System control number |
(OCoLC)929368247 |
| 040 ## - CATALOGING SOURCE |
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| Original cataloging agency |
FlNmELB |
| Language of cataloging |
spa |
| Transcribing agency |
FlNmELB |
| 050 #4 - LIBRARY OF CONGRESS CALL NUMBER |
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| Classification number |
QD151 |
| Item number |
R831 2011 |
| 080 ## - UNIVERSAL DECIMAL CLASSIFICATION NUMBER |
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| Universal Decimal Classification number |
546 |
| 082 04 - DEWEY DECIMAL CLASSIFICATION NUMBER |
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| Classification number |
546 |
| Edition number |
22 |
| 100 1# - MAIN ENTRY--PERSONAL NAME |
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| Personal name |
Rossi, Melina Brenda. |
| 245 10 - TITLE STATEMENT |
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| Title |
Acoplamiento electrónico en compuestos de valencia mixta del grupo VIII, puenteados por cianuro |
| Medium |
[recurso electronico] = |
| Remainder of title |
Electronic coupling in mixed valence cyanide bridged group VIII compounds / |
| Statement of responsibility, etc. |
Melina Brenda Rossi ; director: Luis M. Baraldo Victorica. |
| 246 32 - VARYING FORM OF TITLE |
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| Title proper/short title |
Electronic coupling in mixed valence cyanide bridged group VIII compounds |
| 260 ## - PUBLICATION, DISTRIBUTION, ETC. |
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| Place of publication, distribution, etc. |
Buenos Aires, Argentina : |
| Name of publisher, distributor, etc. |
Universidad de Buenos Aires, |
| Date of publication, distribution, etc. |
2011. |
| 502 ## - DISSERTATION NOTE |
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| Dissertation note |
Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. |
| 520 ## - SUMMARY, ETC. |
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| Summary, etc. |
En este trabajo se desarrolla la síntesis, la caracterización estructural y el estudio de las propiedades espectroscópicas y electroquímicas de una familia de compuestos dinucleares y trinucleares del grupo VIII, puenteados por el ligando cianuro. El objetivo principal es estudiar el acoplamiento electrónico entre los centros metálicos y maximizar dicha interacción, ajustando las variables más determinantes. La reacción directa entre monómeros de Ru(II), conteniendo piridinas de basicidad variable, y un hexacianometalato (III) (Fe(III) o Co(III), da lugar a dímeros de fórmula trans-[(L)RuII(py)4(?-NC)FeIII(CN)5]- y [RuII(DMAP)5(?-NC)MIII(CN)5]-, según la identidad del fragmento central. La interpretación de las propiedades espectroscópicas, haciendo uso del modelo de dos estados de Mulliken - Hush, revela que estos sistemas aumentan la interacción metal - metal, a medida que ambos fragmentos se acercan en energía. Aún así, se observa que todos ellos pertenecen a la Clase II, según la clasificación de Robin - Day, siendo dominante la configuración [RuII-FeIII]. Sin embargo, el comportamiento espectroscópico observado para el dímero [RuII(DMAP)5(?-NC)FeIII(CN)5]- y el trímero de valencia mixta [(CN)5FeII(?-CN)RuII(DMAP)5(?-NC)FeIII(CN)5]5-, en metanol, evidenciando un incremento en la comunicación electrónica entre los centros metálicos, propició la preparación de compuestos conteniendo osmio, bajo el supuesto de que la mayor extensión radial de los orbitales d del osmio incrementaría la mezcla metal - metal. De esta forma, se prepararon y estudiaron los sistemas trinucleares, de fórmula [(CN)5OsIII(?-CN)RuII(DMAP)5(?-NC)MIII(CN)5]4- (M: Co(III), Os(III), Fe(III)). La estructura cristalina de estos compuestos evidencia la presencia de arreglos lineales. Las distancias de enlace en el sistema simétrico sugieren una interacción extendida a lo largo del eje internuclear. Las propiedades espectroscópicas de los sistemas asimétricos revelan que la interacción rutenio - osmio es la que domina. El sistema simétrico, en metanol, presenta un comportamiento próximo a la delocalización electrónica (Clase III). Sin embargo, la especie de valencia mixta no exhibe un incremento en el acoplamiento donor - aceptor, debido a la fuerte interacción entre el fragmento {OsII(CN)5} y el solvente, desacoplando la interacción extendida a lo largo del eje internuclear. Estos resultados establecen un límite de máxima interacción para estos sistemas. |
| 520 ## - SUMMARY, ETC. |
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| Summary, etc. |
This work explores the synthesis, structural caharactarization and the electrochemical and spectroscopic behavior of a family of mixed valence cyanide - bridged dinuclear and trinuclear compounds, containing transition metals of group VIII. The aim of this work is to study the electronic coupling between the metal centres and try to enhance the interaction among them. The reaction of trans-[(L)RuII(py)4Cl]+ or [RuII(DMAP)5(OH)]+complexes with an hexacyanometallate (III) of Fe(III) or Co(III) results in the formation of a family of dinuclear compounds, with molecular formula trans-[(L)RuII(py)4(?-NC)FeIII(CN)5]- or [RuII(DMAP)5(?-NC)MIII(CN)5]-, according to the identity of the ruthenium moiety. The electronic spectroscopy of these compounds show MMCT bands, which are treated according with the Mulliken - Hush two states model approach. Even though results show that the metal - metal interaction is enhanced, as the metal centres come closer, all of these compounds belong to Class II, according to Robin - Day classification, indicating a ground state with [RuII-FeIII] character. However, the spectroscopic behavior of the dinuclear compound [RuII(DMAP)5(?-NC)MIII(CN)5]- as well as the mixed valence trinuclear compound [(CN)5FeII(?-CN)RuII(DMAP)5(?-NC)FeIII(CN)5]5-, in methanol, showing an even higher electronic communication among the metal centres, encouraged the synthesis of a family of trinuclear osmium compounds, with molecular formula [(CN)5OsIII(?-CN)RuII(DMAP)5(?-NC)MIII(CN)5]4- (M: Co(III), Os(III), Fe(III)), given the fact that the more extended osmium d orbitals would give rise to an enhanced mixing between the metal moieties. The crystalline structure of these compounds reveals a linear configuration among the metallic centres. The remarkable bond lengths observed for the symmetric osmium compound suggest an extended metal - metal interaction. The spectroscopic properties of the non - symmetric compounds reveal a higher mixing between the ruthenium - osmium metal moieties. As for the symmetric compound, it ?s behavior in a methanolic solution shows some degree of electronic delocalization. Nevertheless, the mixed valence species does not show an enhanced mixing, due to the stronger interaction among the {OsII(CN)5} moiety and the solvent molecules, precluding the extended electronic communication. These results may settle a higher limit of interaction between these metal moieties. |
| 533 ## - REPRODUCTION NOTE |
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| Type of reproduction |
Recurso electrónico. Santa Fe, Arg.: e-libro, 2015. Disponible vía World Wide Web. El acceso puede estar limitado para las bibliotecas afiliadas a e-libro. |
| 650 #4 - SUBJECT ADDED ENTRY--TOPICAL TERM |
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| Topical term or geographic name entry element |
Química inorgánica. |
| 650 #4 - SUBJECT ADDED ENTRY--TOPICAL TERM |
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| Topical term or geographic name entry element |
Chemistry, Inorganic. |
| 655 #4 - INDEX TERM--GENRE/FORM |
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| Genre/form data or focus term |
Libros electrónicos. |
| 700 1# - ADDED ENTRY--PERSONAL NAME |
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| Personal name |
Baraldo Victorica, Luis M, |
| Relator term |
dir. |
| 710 2# - ADDED ENTRY--CORPORATE NAME |
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| Corporate name or jurisdiction name as entry element |
e-libro, Corp. |
| 856 40 - ELECTRONIC LOCATION AND ACCESS |
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| Uniform Resource Identifier |
<a href="https://elibro.net/ereader/pedagogica/85617">https://elibro.net/ereader/pedagogica/85617</a> |
