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Complexation Equilibria: Factors Influencing Stability of Complexes01:09

Complexation Equilibria: Factors Influencing Stability of Complexes

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In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
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Electrophilic Addition to Alkynes: Halogenation02:38

Electrophilic Addition to Alkynes: Halogenation

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Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
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Properties of Organometallic Compounds01:23

Properties of Organometallic Compounds

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Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
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Acidity of 1-Alkynes02:42

Acidity of 1-Alkynes

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The acidic strength of hydrocarbons follows the order: Alkynes > Alkenes > Alkanes. The strength of an acid is commonly expressed in units of pKa — the lower the pKa, the stronger the acid. Among the hydrocarbons, terminal alkynes have lower pKa values and are, therefore, more acidic. For example, the pKa values for ethane, ethene, and acetylene are 51, 44, and 25, respectively, as shown here.
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Complexation Equilibria: The Chelate Effect01:19

Complexation Equilibria: The Chelate Effect

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In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
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Hydroboration-Oxidation of Alkenes03:08

Hydroboration-Oxidation of Alkenes

10.5K
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
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Alkaline-earth complexes with macrocyclic-functionalised bis(phenolate)s and bis(fluoroalkoxide)s.

Joanna Hammoud1, Fatima Abou-Khalil, Thierry Roisnel

  • 1Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) - UMR 6226, F-35000 Rennes, France. yann.sarazin@univ-rennes1.fr.

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|September 11, 2020
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Summary

Heavy alkaline earth metal complexes with macrocyclic ligands were synthesized and structurally characterized. Ligand modifications influenced coordination, with decreased heteroatoms leading to AeF interactions or dimerization, suggesting low Lewis acidity.

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Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Materials Science

Background:

  • Heavy alkaline earth metals (calcium, strontium, barium) are crucial in various chemical applications.
  • Developing novel ligands for metal complexation is key to tuning reactivity and properties.
  • Macrocyclic ligands offer unique coordination environments for metal ions.

Purpose of the Study:

  • To synthesize and characterize unsolvated molecular complexes of heavy alkaline earths.
  • To investigate the structural features and coordination behavior of these complexes.
  • To explore the influence of ligand structure on metal coordination and Lewis acidity.

Main Methods:

  • Synthesis of heavy alkaline earth metal complexes.
  • X-ray diffraction crystallography for structural determination.
  • Bond valence sum analysis to quantify interactions.
  • Lewis acidity measurements using Childs, Gutmann-Beckett, and electrophilicity index methods.

Main Results:

  • Several families of unsolvated heavy alkaline earth complexes were synthesized.
  • Complexes exhibited seven- or eight-coordinate geometries.
  • Decreased macrocycle heteroatoms led to intramolecular AeF interactions or complex dimerization.
  • Lewis acidity measurements yielded conflicting results, indicating overall low Lewis acidity.

Conclusions:

  • Ligand design significantly impacts the coordination chemistry of heavy alkaline earth metals.
  • Intramolecular AeF interactions and dimerization are strategies to achieve stability in complexes with fewer coordinating heteroatoms.
  • These complexes generally exhibit low Lewis acidity, with no clear trend observed across variations.