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Updated: May 25, 2025

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Published on: January 3, 2018
Promoting π-Facial Interactions in Phenyl-Substituted 1,8-Bis(silylamido)naphthalene Alkaline Earth Complexes
Matthew D Haynes1, Clement G Collins Rice1, Louis J Morris1
1Chemistry Research Laboratory, Department of Chemistry, University of Oxford, 12 Mansfield Road, OX1 3TA Oxford, U.K.
Heavy alkaline earth complexes with rigid bis(amido) ligands were synthesized and characterized. Structural diversity was observed, influenced by ligand substituents and metal ion size, impacting bonding preferences.
Area of Science:
- Organometallic Chemistry
- Coordination Chemistry
- Inorganic Chemistry
Background:
- Alkaline earth metals (Ca, Sr, Ba) are important in various chemical applications.
- Rigid bis(amido) ligands offer unique coordination environments.
- Understanding the structural diversity of these complexes is crucial for their application.
Purpose of the Study:
- To synthesize and characterize novel bimetallic alkaline earth complexes with 1,8-bis(silylamido)naphthalene ligands.
- To investigate the influence of ligand substituents and metal ion size on the structural preferences of these complexes.
- To elucidate the bonding characteristics and structural motifs in these heavy alkaline earth compounds.
Main Methods:
- Synthesis via protonolysis reactions of phenyl-substituted proligands with alkaline earth amide precursors.
- X-ray crystallographic analysis to determine the solid-state structures of the complexes.
- Nuclear Magnetic Resonance (NMR) spectroscopy to study the solution behavior and structural transformations.
- Computational studies to rationalize observed structural trends and bonding.
Main Results:
- Six bimetallic complexes, [(R L)Ae]2, with varying R groups (Ph2Me, Ph3) and alkaline earth metals (Ca, Sr, Ba) were successfully prepared.
- Complexes 1, 2, and 4 exhibited nitrogen-bridged dimer structures, while 5 and 6 showed naphthalene-bridged motifs.
- Complex 3 displayed an intermediate structure, and all complexes converted to monomeric THF adducts in solution.
- Structural diversity was correlated with ligand electronic properties, metal ion size, and metal-ligand bonding strengths.
Conclusions:
- The synthesis of bimetallic alkaline earth complexes with rigid bis(amido) ligands yielded diverse structural outcomes.
- Ligand electronic effects and metal ion characteristics play a significant role in dictating the coordination modes and structural preferences.
- These findings provide valuable insights into the structure-bonding relationships of heavy alkaline earth metal complexes.
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