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Related Concept Videos

Valence Bond Theory02:42

Valence Bond Theory

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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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Formation of Complex Ions03:45

Formation of Complex Ions

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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
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Metallic Solids02:37

Metallic Solids

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Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
All metallic solids exhibit high thermal and electrical conductivity, metallic luster, and malleability....
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Ionic Crystal Structures02:42

Ionic Crystal Structures

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Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
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Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

Crystal Field Theory - Tetrahedral and Square Planar Complexes

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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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Crystal Field Theory - Octahedral Complexes02:58

Crystal Field Theory - Octahedral Complexes

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Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
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Facile CO Cleavage by a Multimetallic CsU2 Nitride Complex.

Marta Falcone1, Christos E Kefalidis2, Rosario Scopelliti1

  • 1Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015, Lausanne, Switzerland.

Angewandte Chemie (International Ed. in English)
|September 7, 2016
PubMed
Summary

Uranium nitride complexes, featuring cesium and bridging nitride ligands, activate the strong carbon-oxygen triple bond under ambient conditions. These multinuclear uranium compounds exhibit unique reactivity, including valence disproportionation, highlighting multimetallic cooperativity.

Keywords:
carbon monoxide cleavagecooperativitynitridesuraniumuranium disproportionation

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Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Materials Science

Background:

  • Uranium nitrides are crucial for nuclear energy and catalysis.
  • The reactivity of molecular uranium nitride compounds is largely unexplored.
  • Understanding the uranium-nitride bond is key to developing new applications.

Purpose of the Study:

  • To investigate the reactivity of a novel uranium nitride complex.
  • To explore the cleavage of strong chemical bonds using uranium nitride compounds.
  • To elucidate the role of multimetallic cooperativity in uranium nitride chemistry.

Main Methods:

  • Synthesis of a cesium uranium nitride complex.
  • Reaction of the complex with carbon monoxide (CO) under ambient conditions.
  • Addition of methyl triflate (MeOTf) to study further reactivity.
  • Computational analysis of reaction mechanisms.

Main Results:

  • The uranium nitride complex readily cleaved the CO bond, forming a [CsU2(μ-CN)(μ-O)] core, demonstrating cation cooperation.
  • Addition of MeOTf induced valence disproportionation of the U(IV) centers to U(III) and U(V) species.
  • Computed mechanisms confirmed the significant role of multimetallic cooperativity in both observed reactions.

Conclusions:

  • A cesium uranium nitride complex exhibits unprecedented reactivity, including CO bond cleavage and valence disproportionation.
  • Multimetallic cooperativity is essential for the observed transformations in these uranium nitride systems.
  • These findings open new avenues for designing functional uranium-based molecular materials.