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Rationalizing oligomerization in dimethylindium(III) chalcogenolates (Me2InER') (E = O, S, Se): a structural and
Glen G Briand1, Andreas Decken, Nathan S Hamilton
1Department of Chemistry and Biochemistry, Mount Allison University, Sackville, New Brunswick, Canada E4L 1G8. gbriand@mta.ca
Dalton Transactions (Cambridge, England : 2003)
|April 8, 2010
Summary
Steric bulk influences the oligomerization of dimethylindium(III) chalcogenolates. Larger substituents lead to monomeric or polymeric structures, unlike dimeric species, showing control over molecular assembly.
Area of Science:
- Organometallic Chemistry
- Coordination Chemistry
- Materials Science
Background:
- Oligomerization in organometallic compounds is crucial for tuning material properties.
- Dimethylindium(III) chalcogenolates offer a versatile platform for studying structural diversity.
- Steric effects are known to influence coordination numbers and aggregation states in metal complexes.
Purpose of the Study:
- To investigate the impact of increasing steric bulk on the oligomerization of dimethylindium(III) chalcogenolates (Me(2)InER', E = O, S, Se).
- To synthesize and characterize a series of these compounds with varying steric hindrance.
- To correlate structural outcomes with the electronic and steric properties of the organic substituents.
Main Methods:
- Synthesis of dimethylindium(III) chalcogenolates via reaction of trimethylindium with phenols, thiophenols, and selenophenols.
- Characterization using elemental analysis, melting point, FT-IR, FT-Raman, solution NMR spectroscopy.
- Determination of solid-state structures through X-ray crystallography.
Main Results:
- Compounds with minimal steric bulk ([Me(2)InOPh](2), [Me(2)InO(2,6-Me(2)C(6)H(3))](2), [Me(2)InSePh](2)) formed dimeric structures.
- Increased steric bulk led to monomeric species (Me(2)InO(2,4,6-tBu(3)C(6)H(3))) or polymeric chains ([Me(2)InS(2,4,6-tBu(3)C(6)H(3))](infinity), [Me(2)InSe(2,4,6-Me(3)C(6)H(3))](infinity), [Me(2)InSe(2,4,6-tBu(3)C(6)H(3))](infinity)).
- The nature of the chalcogen (O, S, Se) and the substituents on indium and the organic ligands significantly influenced the final aggregation state.
Conclusions:
- Steric hindrance is a key factor in controlling the oligomerization of dimethylindium(III) chalcogenolates, dictating monomeric, dimeric, or polymeric structures.
- The methyl substituents on the indium center play a critical role in promoting higher oligomer formation compared to previously studied analogs.
- Theoretical calculations support the observed structural diversity, highlighting the interplay between steric and electronic factors in [R(2)InER'](n) systems.
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