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En Route to a Molecular Terminal Tin Oxide.
Leon Kreßner1, Daniel Duvinage2, Pim Puylaert2
1Institut für Anorganische Chemie, Georg-August-Universität Göttingen, Tammannstraße 4, D-37077 Göttingen, Germany.
Inorganic Chemistry
|April 10, 2024
Summary
Researchers synthesized novel tin complexes with unique ligand arrangements. Steric bulk influenced reactivity, leading to diverse tin selenide and oxide structures, some with unexpected bridging or cyclic formations.
Area of Science:
- Organometallic Chemistry
- Main Group Chemistry
- Inorganic Synthesis
Background:
- Terminal tin chalcogenides are challenging synthetic targets.
- Steric and electronic properties of ligands significantly influence the reactivity of tin complexes.
Purpose of the Study:
- To synthesize novel heteroleptic stannylenes and their corresponding guanidinato complexes.
- To investigate the reactivity of these complexes towards chalcogen sources (selenium and N2O).
- To explore the role of steric protection in controlling reaction outcomes.
Main Methods:
- Synthesis of heteroleptic stannylenes with terphenyl and hexamethyldisilazide ligands.
- Reaction of stannylenes with carbodiimides to form guanidinato complexes.
- Oxidation with elemental selenium and N2O as oxygen transfer reagents.
- Quantum chemical calculations to support structural and reactivity analysis.
Main Results:
- The iso-propyl substituted derivative offered maximum steric protection.
- Oxidation with selenium yielded monomeric terminal tin selenides.
- Reactions with N2O led to silyl migration and terminal tin oxide formation.
- Substitution of silyl groups with cyclohexyl moieties prevented migration, resulting in a tetraselenastannolane with selenium and dimeric compounds with N2O.
Conclusions:
- Steric hindrance is crucial in controlling the formation of terminal tin chalcogenides.
- Ligand design dictates the outcome of reactions with chalcogen transfer reagents.
- Novel cyclic and bridged tin-chalcogen structures were accessed through controlled reactivity.
