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Related Concept Videos

Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate02:21

Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate

Alkenes can be dihydroxylated using potassium permanganate. The method encompasses the reaction of an alkene with a cold, dilute solution of potassium permanganate under basic conditions to form a cis-diol along with a brown precipitate of manganese dioxide.
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide02:44

Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide

Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
Properties of Transition Metals02:58

Properties of Transition Metals

Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.
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...
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids02:04

Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids

Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.
Structural Isomerism02:34

Structural Isomerism

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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Atomic Layer Deposition of Vanadium Dioxide and a Temperature-dependent Optical Model
11:10

Atomic Layer Deposition of Vanadium Dioxide and a Temperature-dependent Optical Model

Published on: May 23, 2018

Non-oxo vanadium(IV) alkoxide chemistry: solid state structures, aggregation equilibria and thermochromic behaviour

Kátia C M Westrup1, Thaiane Gregório, Danilo Stinghen

  • 1Departamento de Química, Universidade Federal do Paraná, Centro Politécnico, 81530-900, Curitiba-PR, Brazil.

Dalton Transactions (Cambridge, England : 2003)
|February 25, 2011
PubMed
Summary

The reversible thermochromic behavior of vanadium(IV) complexes is due to an aggregation equilibrium between dimeric and monomeric species. Bulky groups prevent aggregation, resulting in non-thermochromic mononuclear compounds.

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Atomic Layer Deposition of Vanadium Dioxide and a Temperature-dependent Optical Model
11:10

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Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)
10:42

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)

Published on: December 29, 2016

Area of Science:

  • Inorganic Chemistry
  • Coordination Chemistry
  • Materials Science

Background:

  • Vanadium(IV) complexes exhibit reversible thermochromic behavior in solution.
  • This behavior is linked to aggregation equilibria involving different coordination states.

Purpose of the Study:

  • To investigate the aggregation equilibrium of homoleptic [{V(OR)(4)}(n)] complexes.
  • To understand the role of bulky R groups in preventing aggregation and thermochromism.

Main Methods:

  • Single crystal X-ray diffractometry
  • Magnetic susceptibility measurements
  • Electronic, FTIR, and EPR spectroscopies
  • Variable temperature studies

Main Results:

  • Reversible thermochromism in [{V(OR)(4)}(n)] complexes is attributed to a dimerization equilibrium between five-coordinate dimeric and four-coordinate monomeric vanadium(IV) species.
  • Sterically demanding R groups (e.g., tert-butoxide, tert-pentoxide) inhibit aggregation, yielding non-thermochromic mononuclear complexes.
  • Thermodynamic parameters (equilibrium constants, enthalpy, and entropy changes) for dimerization were quantified.

Conclusions:

  • The study elucidates the molecular mechanism behind the thermochromism of these vanadium complexes.
  • Steric hindrance is a key factor in controlling the aggregation state and resulting properties of vanadium(IV) coordination compounds.