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Related Concept Videos

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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Coordination Compounds and Nomenclature02:54

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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Stereoisomerism02:52

Stereoisomerism

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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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Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

Crystal Field Theory - Tetrahedral and Square Planar Complexes

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Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
49.5K
Coordination Number and Geometry02:57

Coordination Number and Geometry

19.5K
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.
19.5K
EDTA: Chemistry and Properties01:22

EDTA: Chemistry and Properties

3.8K
Polydentate ligands are most widely used in complexometric titrations because they form more stable complexes with the metal ions than mono- or bidentate ligands due to the chelate effect. Examples of polydentate ligands are ethylenediaminetetraacetic acid (EDTA), crown ethers, and cryptands. The most important feature of optimal polydentate ligands is the ability to form 1:1 complexes in a single-step process. Amino carboxylic acid derivatives are frequently used as complexing agents. EDTA is...
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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

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Trapping five-coordinate platinum(iv) intermediates.

Paul A Shaw1, Jessica M Phillips, Guy J Clarkson

  • 1Department of Chemistry, Warwick University, Coventry, UK CV4 7AL. j.rourke@warwick.ac.uk.

Dalton Transactions (Cambridge, England : 2003)
|June 24, 2016
PubMed
Summary
This summary is machine-generated.

Researchers studied the oxidation of platinum(IV) complexes. They found that reaction conditions can trap five-coordinate intermediates, leading to unique cyclometallation products, offering new insights into platinum chemistry.

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Area of Science:

  • Organometallic Chemistry
  • Coordination Chemistry
  • Platinum Catalysis

Background:

  • Cycloplatinated complexes are valuable in catalysis and materials science.
  • Understanding the oxidation mechanisms of platinum(II) complexes is crucial for developing new synthetic routes and catalytic applications.
  • The reactivity of platinum(II) complexes with electrophilic oxidants can lead to platinum(IV) species, but intermediates are often transient.

Purpose of the Study:

  • To investigate the oxidation of doubly cycloplatinated 2,6-di(4-fluorophenyl)pyridine complexes with iodobenzenedichloride.
  • To explore the formation and isolation of five-coordinate platinum intermediates under varying reaction conditions.
  • To characterize the products of these oxidation and trapping reactions, including novel cyclometallated species.

Main Methods:

  • Oxidation reactions using iodobenzenedichloride.
  • Solvent variation and addition of ligating species to trap intermediates.
  • Isolation and characterization of five-coordinate platinum intermediates and final products.
  • Crystallographic analysis of a unique transcyclometallation product.

Main Results:

  • Oxidation of platinum(II) complexes yields trans-dichloro platinum(IV) complexes, which isomerize to cis isomers.
  • Five-coordinate intermediates can be trapped by altering solvent or adding ligands like DMSO or pyridine.
  • The PPr3 derivative forms a five-coordinate species with an agostic interaction, leading to transcyclometallation.
  • A novel complex with singly cyclometallated pyridine and cyclometallated phosphine was characterized crystallographically.

Conclusions:

  • The oxidation of doubly cycloplatinated pyridine complexes is sensitive to reaction conditions, allowing for the isolation of key intermediates.
  • The ability to trap five-coordinate species provides mechanistic insights into platinum oxidation and subsequent reactions.
  • The discovery of transcyclometallation in the PPr3 derivative highlights new pathways for forming complex organometallic structures.