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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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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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Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
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Polydentate ligands are most widely used in complexometric titrations because they form more stable complexes with the metal ions than mono- or bidentate ligands due to the chelate effect. Examples of polydentate ligands are ethylenediaminetetraacetic acid (EDTA), crown ethers, and cryptands. The most important feature of optimal polydentate ligands is the ability to form 1:1 complexes in a single-step process. Amino carboxylic acid derivatives are frequently used as complexing agents. EDTA is...
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Isomerism in Complexes
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The Synthesis of [Sn10SiSiMe334]2- Using a Metastable SnI Halide Solution Synthesized via a Co-condensation Technique
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Enlace de un electrón (2c/1e) estabilizado por los ligandos ortofenilenodiamidos

Kaiyip Chan1, Fei Ying2, Dongyu He1

  • 1Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710069, China.

Journal of the American Chemical Society
|January 19, 2024
PubMed
Resumen

Los investigadores sintetizaron un nuevo compuesto de estaño con el primer enlace sigma de un electrón sin soporte (2c / 1e) estaño-estaño. Este complejo radical estabilizado media las reacciones radicales clave, avanzando la química organometálica.

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Área de la Ciencia:

  • Química organometálica
  • Ciencias de los materiales
  • La Química Radical

Sus antecedentes:

  • Los enlaces de electrones impares, incluidos los enlaces de dos centros, tres electrones (2c / 3e) y un electrón (2c / 1e), son de gran interés debido a sus características únicas de enlace y propiedades radicales.
  • Las especies radicales estabilizadas son intermedios cruciales en varias transformaciones químicas.

Objetivo del estudio:

  • Para sintetizar y caracterizar el primer enlace sin soporte de dos centros, un electrón (2c / 1e) de estaño-estaño sigma.
  • Investigar las propiedades radicales y la reactividad del nuevo complejo de estaño.

Principales métodos:

  • Síntesis del complejo de estaño [K(THF) 6][LSn:··Sn:L] a través de la reducción de estanileno [LSn:] utilizando KC8.
  • Caracterización estructural mediante cristalografía de rayos X.
  • Análisis computacional que emplea la Teoría Funcional de la Densidad (DFT).
  • Espectroscopia de resonancia paramagnética de electrones (EPR).
  • Estudios de reactividad.

Principales resultados:

  • La síntesis exitosa del complejo 1, con el primer enlace 2c/1e Sn··Sn σ sin soporte con una distancia de enlace notable de 3.2155(9) Å.
  • Confirmación del enlace Sn-Sn de un electrón a través de datos cristalográficos, computacionales (DFT) y espectroscópicos (EPR).
  • Demostración de la capacidad del compuesto para actuar como un radical estabilizado deslocalizado sobre dos centros de estaño.

Conclusiones:

  • El complejo de estaño sintetizado representa un avance significativo en el estudio de los enlaces de electrones impares.
  • El compuesto sirve como un mediador eficaz para las reacciones radicales, ejemplificado por el acoplamiento C-C del benzaldehído.
  • Este trabajo abre nuevas vías para explorar la química radical que involucra a los principales elementos del grupo.