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Preparation and Reactions of Sulfides02:26

Preparation and Reactions of Sulfides

Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
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.
Preparation and Reactions of Thiols02:33

Preparation and Reactions of Thiols

Thiols are prepared using the hydrosulfide anion as a nucleophile in a nucleophilic substitution reaction with alkyl halides. For instance, bromobutane reacts with sodium hydrosulfide to give butanethiol.
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.
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.
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...

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Updated: Jun 10, 2026

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
19:58

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Published on: July 30, 2017

Vanadium diaminebis(phenolate) complexes: syntheses, structures, and reactivity in sulfoxidation catalysis.

Sónia Barroso1, Pedro Adão, Filipe Madeira

  • 1Centro de Química Estrutural, Instituto Superior Técnico, TU Lisbon, 1049-001 Lisboa, Portugal.

Inorganic Chemistry
|August 10, 2010
PubMed
Summary

New vanadium complexes show high selectivity in thioanisole sulfoxidation using hydrogen peroxide. However, these catalysts do not provide enantioselectivity in the reaction.

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Area of Science:

  • Coordination Chemistry
  • Organometallic Chemistry
  • Catalysis

Background:

  • Vanadium complexes with diaminebis(phenolate) ligands are synthesized and characterized.
  • The general formulas [LVCl(THF)] and [LV(O)X] describe the synthesized vanadium(V) complexes.
  • All synthesized compounds exhibit octahedral geometry with trans-O(Ph) coordination.

Purpose of the Study:

  • To synthesize and characterize novel vanadium diaminebis(phenolate) complexes.
  • To investigate the catalytic activity of these complexes in thioanisole sulfoxidation.
  • To explore the potential for enantioselectivity in the catalytic oxidation reactions.

Main Methods:

  • Synthesis and characterization of vanadium complexes using spectroscopic techniques (NMR, UV-vis, circular dichroism).
  • Catalytic testing of vanadium complexes in thioanisole sulfoxidation using hydrogen peroxide as the oxidant.
  • Investigation of reaction mechanisms and solvent interactions using (1)H and (51)V NMR spectroscopy.

Main Results:

  • Novel vanadium(V) complexes with diaminebis(phenolate) ligands were successfully synthesized and characterized.
  • The complexes demonstrated high selectivity in thioanisole sulfoxidation with H(2)O(2) as the oxidant.
  • No enantioselectivity was observed, even with enantiopure catalyst precursors.
  • NMR studies revealed complex reactions with solvents and the formation of peroxovanadium species.

Conclusions:

  • Vanadium diaminebis(phenolate) complexes are effective catalysts for selective thioanisole sulfoxidation.
  • The catalytic system shows high selectivity but lacks enantioselectivity.
  • Further mechanistic studies are needed to understand the solvent interactions and peroxovanadium formation.