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Structural Isomerism02:34

Structural Isomerism

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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...
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Isomers are molecules with the same molecular formula but different structural arrangements. Isomers can be further classified into constitutional isomers and stereoisomers. Constitutional isomers differ in the connectivity of their constituent atoms. For example, 2-butanol and diethyl ether are constitutional isomers, as they have the same chemical formula, C4H10O, but differ in the connectivity of the carbon and oxygen atoms. Constitutional isomers have different physical and chemical...
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Isomerism in Alkenes02:01

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Alkenes like 1-butene and 2-butene exhibit constitutional isomerism, as they differ in the position of the double bond. Further, 2-butene exhibits stereoisomerism and exists as two distinct compounds differing in spatial arrangement.
An isomer is called cis-2-butene when the methyl groups are on the same side of the double bond, and the other stereoisomer, in which methyl groups are on the opposite side of the double bond, is called trans-2-butene. The cis and trans stereoisomers are not...
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Controller Configurations01:22

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Controller configurations are crucial in a car's cruise control system because they manage speed over time to maintain a consistent pace regardless of road conditions, thereby meeting design goals. In traditional control systems, fixed-configuration design involves predetermined controller placement. System performance modifications are known as compensation.
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Electron Configurations02:46

Electron Configurations

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Electron configurations and orbital diagrams can be determined by applying the Aufbau principle (each added electron occupies the subshell of lowest energy available), Pauli exclusion principle (no two electrons can have the same set of four quantum numbers), and Hund’s rule of maximum multiplicity (whenever possible, electrons retain unpaired spins in degenerate orbitals).
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The alkali metal sodium (atomic number 11) has one more electron than the neon atom. This electron must go into the lowest-energy subshell available, the 3s orbital, giving a 1s22s22p63s1 configuration. The electrons occupying the outermost shell orbital(s) (highest value of n) are called valence electrons, and those occupying the inner shell orbitals are called core electrons. Since the core electron shells correspond to noble gas electron configurations, we can abbreviate electron...
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Configurational Isomerism in Polyoxovanadates.

Lisa K Mahnke1, Aleksandar Kondinski2,3, Ulrike Warzok4

  • 1Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, 24118, Kiel, Germany.

Angewandte Chemie (International Ed. in English)
|January 13, 2018
PubMed
Summary
This summary is machine-generated.

Researchers discovered a unique reaction in polyoxovanadate clusters involving antimony, leading to a novel, high-energy isomer. This finding sheds light on cluster rearrangements driven by supramolecular interactions.

Keywords:
DFT calculationsESI MSantimonato polyoxovanadatesconfigurational isomerismpolyoxometalates

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Area of Science:

  • Inorganic Chemistry
  • Supramolecular Chemistry
  • Materials Science

Background:

  • Polyoxovanadates are versatile inorganic clusters with diverse structures.
  • Understanding cluster rearrangements is key to designing new materials.
  • Supramolecular interactions play a crucial role in self-assembly and reactivity.

Purpose of the Study:

  • To investigate cluster shell rearrangements in polyoxovanadates driven by supramolecular interactions.
  • To explore a unique reaction pathway involving antimony (Sb) in polyoxovanadate clusters.
  • To characterize a novel metastable configurational isomer of the {V14Sb8O42} cluster.

Main Methods:

  • Ligand metathesis using peripheral [Ni(ethylenediamine)3]2+ counterions.
  • Isolation and characterization of the {V14Sb8O42} cluster isomers.
  • X-ray diffraction for solid-state structure determination.
  • Electrospray Ionization Mass Spectrometry (ESI-MS) for solution and gas-phase analysis.
  • Density Functional Theory (DFT) calculations for energetic and structural insights.

Main Results:

  • A unique Sb-specific reaction was induced by ligand metathesis, forming the metastable α1* isomer of {V14Sb8O42}.
  • The α1* isomer exhibits an unusual inward-oriented vanadyl group and is energetically higher than known isomers.
  • Supramolecular Sb-O···V and Sb-O···Sb contacts stabilize {V14Sb8O42}2 dimers in the solid state.
  • ESI-MS confirmed the stability of these dimers in solution and gas phases.
  • DFT calculations suggest the potential accessibility of other elusive {V14Sb8} isomers.

Conclusions:

  • Supramolecular interactions can drive unexpected cluster shell rearrangements in polyoxovanadates.
  • The discovery of the α1* isomer and its associated dimers expands the known structural diversity of polyoxovanadates.
  • This work provides a foundation for exploring new reaction pathways and designing novel polyoxovanadate-based materials.