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Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate
Published on: February 23, 2016
Organic-soluble tri-, tetra-, and pentanuclear titanium(IV) phosphates
Ramaswamy Murugavel1, Subramaniam Kuppuswamy
1Department of Chemistry and Centre for Research in Nanotechnology and Science, Indian Institute of Technology-Bombay, Powai, Mumbai-400076, India. rmv@chem.iitb.ac.in
Inorganic Chemistry
|July 30, 2008
Summary
Bulky aryl phosphate ligands react with titanium precursors to form novel titanophosphate cages. Different ligands and titanium sources yield distinct multinuclear structures, revealing insights into titanium-oxygen cluster formation.
Area of Science:
- Organometallic Chemistry
- Inorganic Chemistry
- Materials Science
Background:
- Titanophosphate cages are of interest due to their unique structural motifs and potential applications.
- The reactivity of bulky aryl phosphates with titanium precursors is not fully understood.
Purpose of the Study:
- To investigate the reaction of bulky 2,6-disubstituted aryl phosphates with titanium precursors.
- To synthesize and characterize novel titanophosphate clusters.
- To elucidate the structural diversity and formation pathways of these clusters.
Main Methods:
- Reactions of 2,6-dimethylphenyl phosphate (dmppH 2) and 2,6-diisopropylphenyl phosphate (dippH 2) with Cp*TiCl 3 and Ti(O iPr) 4.
- Isolation and characterization of products by single crystal X-ray diffraction.
- Spectroscopic analysis including IR and NMR (1H and 31P).
- Elemental analysis.
Main Results:
- The reaction of dippH 2 with Cp*TiCl 3 yielded a trinuclear titanophosphate cage (1).
- The reaction of dmppH 2 with Cp*TiCl 3 yielded a tetranuclear titanophosphate cage (2).
- Using Ti(O iPr) 4 with dippH 2 resulted in a pentanuclear titanophosphate (3).
- Compounds 1-3 were isolated in good yields (59-75%) and characterized structurally.
Conclusions:
- The steric bulk of aryl phosphate ligands and the choice of titanium source significantly influence the nuclearity and structure of the resulting titanophosphate clusters.
- Cp*-Ti bond cleavage is observed in the formation of clusters 1 and 2.
- A common Ti-O-Ti dimeric building block is proposed as a precursor for all three clusters, suggesting a unified formation mechanism.
