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Valence Bond Theory02:42

Valence Bond Theory

Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...
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The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
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In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
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When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human eye.

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Complejos de hidruro de cobalto de tres y cuatro coordenadas que reaccionan con dinitrógeno.

Keying Ding1, William W Brennessel, Patrick L Holland

  • 1Department of Chemistry, University of Rochester, Rochester, New York 14618, USA.

Journal of the American Chemical Society
|July 23, 2009
PubMed
Resumen

Los investigadores sintetizaron nuevos complejos de hidruro de cobalto utilizando ligandos beta-diketiminados voluminosos. Estos complejos reaccionan con el gas nitrógeno (N(2) para formar nuevos complejos dinucleares de nitrógeno, liberando gas hidrógeno (H(2)).

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Área de la Ciencia:

  • Química organometálica Química orgánica de los metales.
  • Coordinación Química de la Coordinación
  • Química Inorgánica La Química Inorgánica es la química inorgánica.

Sus antecedentes:

  • Los ligandos beta-diketiminados voluminosos son cruciales para la estabilización de los centros metálicos reactivos.
  • Los complejos de hidruro de cobalto son de interés por su potencial catalítico y su reactividad única.
  • Comprender el entorno de coordinación de los metales de transición es clave para diseñar nuevos complejos.

Objetivo del estudio:

  • Para sintetizar y caracterizar nuevos complejos de hidruro de cobalto soportados por voluminosos ligandos beta-diketiminados.
  • Para investigar la reactividad de estos complejos de hidruro de cobalto con el gas nitrógeno (N(2)).
  • Para explorar la formación de complejos de nitrógeno dinuclear y la liberación de hidrógeno.

Principales métodos:

  • Síntesis de complejos de hidruro de cobalto a través de la reacción de LCoCl con trietilborohidruro de potasio.
  • Caracterización cristalográfica de los complejos resultantes de hidruro de cobalto dinuclear.
  • Reacción de los complejos de hidruro de cobalto con el gas nitrógeno a temperatura ambiente.

Principales resultados:

  • Formación de dos nuevos complejos de hidruro de cobalto, [LCo(mu-H) ](2) (1) y K(2) [LCoH](2) (2), dependiendo de las condiciones de reacción.
  • El Compuesto 2 representa el primer complejo de hidruro de metal de transición de tres coordenadas caracterizado cristalográficamente.
  • Ambos complejos reaccionan con N(2) para producir complejos dinucleares N(2) con la evolución de H(2).

Conclusiones:

  • Los ligandos voluminosos de beta-diketiminato apoyan efectivamente la formación de especies únicas de hidruro de cobalto.
  • Los nuevos complejos de hidruro de cobalto exhiben reactividad hacia N(2), lo que lleva a la formación de complejos de nitrógeno dinucleares.
  • Este trabajo amplía la comprensión de la reactividad del hidruro de metal de transición y la química de fijación de nitrógeno.