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Related Concept Videos

Metal-Ligand Bonds02:51

Metal-Ligand Bonds

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The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
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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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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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Crystal Field Theory - Octahedral Complexes02:58

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Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
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Valence Bond Theory02:42

Valence Bond Theory

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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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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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Application of Elemental Lanthanides in the Selective C-F Activation of Trifluoromethylated Benzofulvenes Providing Access to Various Difluoroalkenes
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Application of Elemental Lanthanides in the Selective C-F Activation of Trifluoromethylated Benzofulvenes Providing Access to Various Difluoroalkenes

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C-H bond activation by f-block complexes.

Polly L Arnold1, Max W McMullon, Julia Rieb

  • 1EaStCHEM School of Chemistry, University of Edinburgh, The King's Buildings, Edinburgh, EH9 3FJ (UK); Institute for Advanced Study, Technische Universität München, Lichtenbergstrasse 2a, 85748 Garching (Germany). Polly.Arnold@ed.ac.uk.

Angewandte Chemie (International Ed. in English)
|November 12, 2014
PubMed
Summary

Lanthanide complexes show promise for catalyzing C-H bond activation, a key step in chemical synthesis. Further research is needed to fully close catalytic cycles for efficient value-added product generation.

Keywords:
actinidesasymmetric catalysispolarity reversal catalysisradical additionrare earths

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Area of Science:

  • Organometallic chemistry
  • Catalysis
  • Lanthanide chemistry

Background:

  • Homogeneous catalysis often involves designing metal complexes for substrate conversion.
  • Organometallic lanthanide complexes were early pioneers in catalytic C-H bond transformation.
  • Selective C-H bond cleavage in methane was demonstrated by lanthanide methyl complexes 25 years ago.

Purpose of the Study:

  • To explore the potential of f-block complexes in catalytic C-H bond activation.
  • To address the challenges in closing catalytic cycles for hydrocarbon transformations.
  • To highlight the significance of lanthanide compounds in catalysis.

Main Methods:

  • Design and synthesis of organometallic lanthanide complexes.
  • Investigation of catalytic activity in C-H bond activation.
  • Analysis of reaction mechanisms to understand catalytic cycle closure.

Main Results:

  • Demonstrated selective C-H bond cleavage in methane using specific lanthanide complexes.
  • Identified numerous metal complexes capable of hydrocarbon C-H bond activation.
  • Observed significant potential in f-block complexes for these transformations.

Conclusions:

  • Lanthanide complexes offer a promising avenue for C-H bond activation catalysis.
  • Closing catalytic cycles remains a key challenge in this field.
  • F-block elements hold considerable potential for advancing hydrocarbon chemistry.