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Metal-Ligand Bonds02:51

Metal-Ligand Bonds

20.7K
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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Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide02:44

Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide

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Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
10.1K
Complexometric Titration: Ligands00:43

Complexometric Titration: Ligands

948
Different monodentate and polydentate ligands are used as complexing agents in complexometric titration reactions. The formation of complexes by mono- and bidentate ligands involves two or more intermediate steps, limiting their use as complexing agents. In comparison, polydentate ligands can form complexes with metal ions in a single-step process, facilitating sharper end points. This means polydentate ligands, such as amino carboxylic acid derivatives, are most commonly employed in...
948
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation02:17

Reduction of Alkenes: Asymmetric Catalytic Hydrogenation

3.3K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
3.3K
EDTA: Chemistry and Properties01:22

EDTA: Chemistry and Properties

1.9K
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...
1.9K
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction01:22

Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction

1.9K
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.
1.9K

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Updated: Jun 27, 2025

Catalytic Reactions at Amine-Stabilized and Ligand-Free Platinum Nanoparticles Supported on Titania During Hydrogenation of Alkenes and Aldehydes
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Catalytic Reactions at Amine-Stabilized and Ligand-Free Platinum Nanoparticles Supported on Titania During Hydrogenation of Alkenes and Aldehydes

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Modeling Complex Ligands for High Oxidation State Catalysis: Titanium Hydroamination with Unsymmetrical Ligands.

Zhilin Hou1, Rashmi Jena1, Tanner J McDaniel1

  • 1Department of Chemistry, Michigan State University, 578 S. Shaw Ln, East Lansing, Michigan 48824, United States.

ACS Catalysis
|April 25, 2024
PubMed
Summary

This study models titanium-catalyzed alkyne hydroamination using unsymmetrical ligands. The ligand donor parameter and percent buried volume predict catalyst performance, leading to new, highly active catalysts.

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Area of Science:

  • Organometallic Chemistry
  • Catalysis
  • Homogeneous Catalysis

Background:

  • Titanium complexes are effective catalysts for alkyne hydroamination.
  • Understanding ligand effects is crucial for optimizing catalyst performance.
  • Bidentate ligands offer tunable electronic and steric properties.

Purpose of the Study:

  • To develop a model for predicting catalytic activity based on ligand properties.
  • To investigate how unsymmetrical bidentate ligands influence titanium-catalyzed hydroamination.
  • To design novel precatalysts with enhanced reactivity.

Main Methods:

  • Synthesis of seven new unsymmetrical titanium precatalysts with pyrrolyl/indolyl linkages.
  • Application of a quantitative model using ligand donor parameter (LDP) and percent buried volume (% Vbur).
  • Kinetic studies correlating observed rates (kobs) with ligand electronic and steric parameters.

Main Results:

  • The model successfully correlates catalyst structure with reactivity.
  • Ligand attachment points exhibit distinct electronic and steric environments.
  • Catalyst performance is governed by a combination of electronic and steric factors from both ligand sides.

Conclusions:

  • Unsymmetrical ligands can be strategically designed for improved catalytic outcomes.
  • Electronic factors primarily dictate ligand positioning, while sterics influence activity.
  • The developed model enables the rational design of highly efficient titanium hydroamination catalysts.