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Updated: Jun 8, 2026

Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate

Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate

Published on: February 23, 2016

Optically active bis(β-diketonate) complexes of titanium.

Natcharee Kongprakaiwoot¹, Jack B Armstrong, Bruce C Noll

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

Dalton Transactions (Cambridge, England : 2003)

|September 11, 2010

Summary

This summary is machine-generated.

Chiral titanium diketonate complexes, (Tol(2)Bob)Ti(IV), were synthesized and resolved using BINOL ligands. These complexes exhibit stability towards racemization, with potential for identifying metal center configuration via circular dichroism.

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Area of Science:

Organometallic Chemistry
Stereochemistry
Coordination Chemistry

Background:

Titanium(IV) complexes with bis(diketonate) ligands are of interest for their structural and stereochemical properties.
Chiral ligands are crucial for inducing asymmetry in metal complexes.
Understanding racemization pathways is key for developing stable chiral catalysts.

Purpose of the Study:

To synthesize and resolve novel chiral titanium(IV) bis(diketonate) complexes.
To investigate the stereochemical stability and racemization behavior of these complexes.
To explore the utility of circular dichroism in determining the configuration of titanium centers.

Main Methods:

Reaction of titanium isopropoxide with chiral 1,1'-bi-2-naphthol (BINOL) and bis(diketonate) ligands.
Ligand cleavage using trifluoromethanesulfonic acid.
Racemization studies under varying conditions (temperature, protic environments).
Circular dichroism (CD) spectroscopy for configuration determination.

Main Results:

Successful synthesis and resolution of (S,Δ)-(Tol(2)Bob)Ti(R-BINOL) and related complexes.
The (Tol(2)Bob)Ti(IV) fragment demonstrated significant stability towards racemization (half-life > 34 h at 51 °C).
Protic conditions were found to accelerate racemization, likely via protonolysis.
Distinct CD signals were observed, correlating with the titanium center's configuration.
A single diastereomer was formed using a chiral binaphthyl-bridged ligand.

Conclusions:

Optically active titanium bis(diketonate) fragments can be prepared with controlled stereochemistry.
The (Tol(2)Bob)Ti(IV) fragment exhibits notable kinetic stability against racemization.
Circular dichroism spectroscopy is a valuable tool for assigning the absolute configuration of titanium centers in these complexes.