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Coordination Compounds and Nomenclature

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In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
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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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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.
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The half-life of a reaction (t1/2) is the time required for one-half of a given amount of reactant to be consumed. In each succeeding half-life, half of the remaining concentration of the reactant is consumed. For example, during the decomposition of hydrogen peroxide, during the first half-life (from 0.00 hours to 6.00 hours), the concentration of H2O2 decreases from 1.000 M to 0.500 M. During the second half-life (from 6.00 hours to 12.00 hours), the concentration decreases from 0.500 M to...
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Coordination Number and Geometry

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For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
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Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
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Preparation of SNS CobaltII Pincer Model Complexes of Liver Alcohol Dehydrogenase
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Cobalt bis(acetylacetonate)-

Xiaoshen Ma1, Seth B Herzon1,2

  • 1Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.

Beilstein Journal of Organic Chemistry
|September 12, 2018
PubMed
Summary

A new cobalt catalyst system enables efficient alkene hydrofunctionalization and reductive couplings. This inexpensive reagent combination offers a practical approach for developing hydrogen atom transfer (HAT) reactions.

Keywords:
HAThydrofunctionalizationhydrogen atom transfer

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Area of Science:

  • Organic Chemistry
  • Catalysis

Background:

  • Alkene hydrofunctionalization is crucial in organic synthesis.
  • Developing efficient and general catalytic methods remains an active area of research.

Purpose of the Study:

  • To introduce a novel, cost-effective reagent system for Markovnikov-selective alkene hydrofunctionalization.
  • To explore new applications of hydrogen atom transfer (HAT) in organic transformations.

Main Methods:

  • Utilized cobalt bis(acetylacetonate) [Co(acac)2], tert-butyl hydroperoxide (TBHP), and triethylsilane (Et3SiH) as a reagent combination.
  • Investigated the mechanism involving cobalt-mediated hydrogen atom transfer (HAT) and radical intermediate interception.

Main Results:

  • Demonstrated the initiation of a broad range of Markovnikov-selective alkene hydrofunctionalization reactions.
  • Reported the first reductive couplings of unactivated alkenes and aryldiazonium salts via an HAT pathway.

Conclusions:

  • The Co(acac)2-TBHP-Et3SiH system is an inexpensive, general, and practical reagent combination.
  • This methodology provides a versatile platform for developing HAT reactions in complex molecular settings.