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The Synthesis of [Sn10SiSiMe334]2- Using a Metastable SnI Halide Solution Synthesized via a Co-condensation Technique
Published on: November 28, 2016
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Heteroallene Insertions into Tin(II) Alkoxide Bonds.
Aidan T Ryan1, Andrew Brookes1,2, Andrew J Straiton1
1Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom.
Inorganic Chemistry
|June 4, 2024
Summary
Tin(II) alkoxide reactions with isocyanates yield novel iso-carbamate complexes. Carbon dioxide insertion into tin(II) alkoxides forms reversible alkyl carbonates, with detailed kinetic studies providing activation parameters.
Area of Science:
- Organometallic Chemistry
- Coordination Chemistry
- Synthetic Inorganic Chemistry
Background:
- Tin(II) alkoxides are versatile precursors in organometallic synthesis.
- Isocyanates are reactive species capable of undergoing insertion reactions.
- Understanding the reactivity of tin(II) compounds with unsaturated molecules is crucial for developing new synthetic methodologies.
Purpose of the Study:
- To synthesize and characterize novel iso-carbamate complexes derived from tin(II) alkoxides and isocyanates.
- To investigate the solution-state behavior and reaction mechanisms of these complexes.
- To explore the potential for carbon dioxide insertion into tin(II) alkoxides and characterize the resulting products.
Main Methods:
- Synthesis of iso-carbamate complexes via reactions of tin(II) alkoxides with aryl and alkyl isocyanates.
- Structural characterization of complexes using X-ray diffraction.
- Solution-state chemistry investigated by 1H DOSY and 1H NMR spectroscopy.
- Kinetic studies using Variable-Temperature 2D 1H-1H Exchange Spectroscopy (VT-2D-EXSY).
Main Results:
- Mono-insertion of aryl isocyanates yielded dimeric iso-carbamate complexes.
- Bis-insertion of alkyl isocyanates formed monomeric iso-carbamate complexes, with several structurally characterized.
- Reversible mono-insertion of tert-butyl isocyanate was observed, with kinetic parameters determined.
- Carbon dioxide insertion into tin(II) alkoxides was unsuccessful, but a new Sn(II) alkyl carbonate species was identified and its reversible formation studied kinetically.
Conclusions:
- Tin(II) alkoxides react with isocyanates to form structurally diverse iso-carbamate complexes, with reaction outcomes dependent on the nature of the isocyanate (aryl vs. alkyl).
- The study provides detailed kinetic insights into the reversible insertion of tert-butyl isocyanate and the formation of tin(II) alkyl carbonates.
- The findings contribute to the understanding of tin(II) reactivity and offer potential pathways for novel organotin compound synthesis.
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