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Consequence of Ligand Bite Angle on Bismuth Lewis Acidity
Ramkumar Kannan1, Sandeep Kumar2, Alex P Andrews1
1School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram , Vithura, Thiruvananthapuram 695551, India.
Inorganic Chemistry
|August 10, 2017
Summary
Researchers explored ligand bite angles in main-group chemistry for the first time, using organobismuth cations to tune Lewis acidity. A shorter bite angle in a specific ligand resulted in significantly higher Lewis acidity.
Area of Science:
- Organometallic Chemistry
- Main-Group Chemistry
- Lewis Acidity
Background:
- Ligand bite angle is a key parameter for tuning reactivity in transition-metal chemistry.
- Its application in main-group chemistry, particularly for controlling Lewis acidity, remains largely unexplored.
- Organobismuth cations offer a promising platform for investigating such effects.
Purpose of the Study:
- To investigate the influence of ligand bite angle on Lewis acidity in organobismuth cations.
- To introduce the concept of controlling Lewis acidity through ligand design in main-group chemistry.
- To quantify the Lewis acidity of novel organobismuth compounds.
Main Methods:
- Synthesis of organobismuth cations featuring 2-[(dimethylamino)methyl]phenyl and 2-(dimethylamino)phenyl ligands.
- Structural analysis to determine C-Bi-N bite angles.
- Application of the Gutmann-Beckett method for Lewis acidity quantification.
Main Results:
- The 2-(dimethylamino)phenyl ligand induced a shorter C-Bi-N bite angle compared to the 2-[(dimethylamino)methyl]phenyl ligand.
- A shorter bite angle correlated with a weaker Bi-N bond and a lower-energy Bi-N σ*-acceptor orbital.
- Organobismuth cations with shorter bite angles exhibited significantly higher Lewis acidity.
Conclusions:
- Ligand bite angle is a viable strategy for tuning Lewis acidity in main-group organometallic chemistry.
- The C-Bi-N bite angle directly influences the electronic properties and Lewis acidity of organobismuth cations.
- This study successfully quantifies Lewis acidity in organobismuth cations using the Gutmann-Beckett method, opening new avenues for catalyst design.
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