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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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Complexation Equilibria: The Chelate Effect01:19

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In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
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Reduction of Alkynes to trans-Alkenes: Sodium in Liquid Ammonia02:10

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Alkynes can be reduced to trans-alkenes using sodium or lithium in liquid ammonia. The reaction, known as dissolving metal reduction, proceeds with an anti addition of hydrogen across the carbon–carbon triple bond to form the trans product. Since ammonia exists as a gas (bp = −33°C) at room temperature, the reaction is carried out at low temperatures using a mixture of dry ice (sublimes at −78°C) and acetone. 
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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.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
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A sizable fraction of proteins destined for ER are first synthesized in the cell cytosol and then transported across the ER membrane–a process called post-translational translocation. Similar to cotranslationally translocated proteins, these proteins also use the Sec translocon complex to enter the ER lumen.
Targeting proteins to the ER
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The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
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Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
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Transelementación B/Al inesperada dentro de un complejo de pinzas Rh

Qingheng Lai1, Nattamai Bhuvanesh1, Oleg V Ozerov1

  • 1Department of Chemistry, Texas A&M University, 3255 TAMU, College Station, Texas 77842, United States.

Journal of the American Chemical Society
|December 2, 2020
PubMed
Resumen

Los investigadores sintetizaron complejos de pinzas de rodio con centros de aluminio o boro. Se produjo una metástasis B/Al inesperada al tratar de modificar el sitio de aluminio, produciendo un complejo de boro en su lugar.

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Área de la Ciencia:

  • Química organometálica
  • Química de coordinación
  • Química del grupo principal

Sus antecedentes:

  • Los complejos de pinzas ofrecen una reactividad única debido a su coordinación tridentada.
  • El aluminio y el boro son elementos clave en el grupo principal y la química organometálica, respectivamente.
  • Comprender la estabilización y la reactividad de los elementos del grupo principal de baja coordinación es crucial.

Objetivo del estudio:

  • Síntesis y caracterización de nuevos complejos de pinzas de rodio con unidades de bis (N-pirrolil) aluminila (PAlP) y borilo (PBP).
  • Para investigar la reactividad del sitio de aluminilo en el complejo de rodio PAlP.
  • Explorar métodos para acceder a centros de aluminio de tres coordenadas dentro de un marco de pinzas.

Principales métodos:

  • Síntesis de los complejos dicarbonílicos de PAlP y PBP.
  • Coordinación de la piridina para estabilizar el sitio de aluminilo en (PAlpyP) Rh (CO) 2.
  • Reacciones que involucran la abstracción de piridina mediada por ácido de Lewis utilizando BF3·Et2O y B(C6F5) 3.

Principales resultados:

  • Síntesis exitosa de (PAlpyP) Rh (CO) 2 con un centro de aluminio de cuatro coordenadas estabilizado por piridina.
  • Se produjo una metátesis B/Al inesperada tras el tratamiento con BF3· Et2O, formando el complejo (PBP) RhCO mientras se conservaba la estructura de la pinza.
  • El intento de abstracción de piridina con B ((C6F5) 3 condujo a la dimerización del complejo PAlP a través del puente de isocarbonio.

Conclusiones:

  • La coordinación de la piridina es efectiva para estabilizar un sitio de aluminila de cuatro coordenadas en complejos de pinzas de rodio.
  • Las reacciones mediadas por el ácido de Lewis pueden inducir una metátesis B/Al inesperada, ofreciendo una ruta alternativa a los complejos de boro.
  • La reactividad del complejo de pinzas de aluminio es sensible al agente de abstracción, lo que lleva a la dimerización bajo ciertas condiciones.