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Rational synthesis of normal, abnormal and anionic NHC-gallium alkyl complexes: structural, stability and
Marina Uzelac1, Alberto Hernán-Gómez1, David R Armstrong1
1WestCHEM , Department of Pure and Applied Chemistry , University of Strathclyde , Glasgow , G1 1XL , UK .
Chemical Science
|June 19, 2018
Summary
This study synthesizes novel gallium complexes with N-heterocyclic carbene (NHC) ligands, revealing new pathways for creating abnormal NHC complexes. These findings advance the rational design of main-group NHC compounds.
Area of Science:
- Organometallic Chemistry
- Main-Group Chemistry
- Carbene Chemistry
Background:
- N-heterocyclic carbenes (NHCs) are versatile ligands in organometallic chemistry.
- Rational design of main-group NHC complexes is crucial for advancing catalysis and materials science.
- Understanding ligand behavior in metal complexes is key to controlling reactivity.
Purpose of the Study:
- To synthesize and characterize novel gallium complexes featuring normal and abnormal N-heterocyclic carbene ligands.
- To investigate the reactivity of anionic NHC-gallate species and explore pathways to abnormal NHC complexes.
- To elucidate the mechanism of thermal isomerization between normal and abnormal NHC-gallium complexes.
Main Methods:
- Synthesis and X-ray crystallographic characterization of gallium-NHC complexes.
- Nuclear Magnetic Resonance (NMR) spectroscopy for structural elucidation.
- Electrophilic interception studies and kinetic experiments.
- Density Functional Theory (DFT) calculations.
Main Results:
- Novel neutral and anionic NHC-gallium complexes were synthesized, including a gallate species with a bridging NHC ligand.
- Electrophilic attack on the gallate species preferentially occurred at the C2 position of the NHC ligand.
- A thermally induced rearrangement of a normal NHC-gallium complex to its abnormal isomer was observed and mechanistically studied.
- DFT calculations and kinetic studies suggest a dissociative mechanism for the isomerization, influenced by solvent and steric factors.
Conclusions:
- The study provides new synthetic routes to abnormal NHC-gallium complexes.
- The findings highlight the tunable reactivity of NHC ligands in main-group organometallic chemistry.
- Steric relief is identified as a key driving force for the isomerization to abnormal NHC complexes, offering insights for future ligand design.
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