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Related Concept Videos

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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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,...
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Formation of Complex Ions

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...
Properties of Transition Metals02:58

Properties of Transition Metals

Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.
Metal-Ligand Bonds02:51

Metal-Ligand Bonds

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.
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Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction01:22

Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction

The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.

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Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
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Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene

Published on: March 20, 2017

Intermetallic communication in titanium(IV) ferrocenyldiketonates.

Lea T Dulatas1, Seth N Brown, Edema Ojomo

  • 1Department of Chemistry and Biochemistry, 251 Nieuwland Science Hall, University of Notre Dame, Notre Dame, Indiana 46556-5670, USA.

Inorganic Chemistry
|October 23, 2009
PubMed
Summary

A new titanium complex with a ferrocenyldiketonate ligand was synthesized and characterized. Its color and redox properties change with different anions, indicating titanium

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Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate
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Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate
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Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate

Published on: February 23, 2016

Area of Science:

  • Organometallic Chemistry
  • Coordination Chemistry
  • Materials Science

Background:

  • Ferrocene-based ligands offer unique redox and electronic properties.
  • Tetradentate ligands can stabilize various metal centers.
  • Titanium complexes are versatile in catalysis and materials.

Purpose of the Study:

  • Synthesize and characterize a novel tetradentate bis(ferrocenyldiketonate) titanium complex.
  • Investigate the influence of different exogenous groups on the complex's properties.
  • Explore the electronic interactions between the titanium center and the ferrocene moieties.

Main Methods:

  • Claisen condensation for ligand synthesis.
  • Metalation with titanium(IV) isopropoxide.
  • Anion metathesis and hydrolysis reactions.
  • X-ray crystallography for structural determination.
  • UV-Vis spectroscopy and cyclic voltammetry.
  • Density-functional theory (DFT) calculations.

Main Results:

  • Successful synthesis of the (Fc(2)Bob)Ti(O(i)Pr)(2) complex and its derivatives.
  • Formation of a mu-oxo trimer and a bis(o-hydroxyphenoxide) complex.
  • Structures reveal ferrocene groups proximal to the biphenyl backbone.
  • Dramatic color changes observed with varying anions (red to green).
  • Modest shifts in ferrocene oxidation potentials, with limited separation.
  • DFT calculations suggest Ti primarily interacts with the ferrocene LUMO.

Conclusions:

  • The synthesized ferrocenyldiketonate ligand effectively coordinates titanium.
  • The titanium center's environment significantly influences the complex's optical and redox properties.
  • Electronic communication between Ti and ferrocene is primarily through the LUMO.
  • The structural orientation of ferrocene units impacts intermolecular interactions.