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Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
Electrophilic attack on trinuclear titanium imido-nitrido systems.
Jorge Caballo1, Mariano González-Moreiras, Miguel Mena
1Departamento de Química Inorgánica, Universidad de Alcalá, 28871 Alcalá de Henares-Madrid, Spain.
Dalton Transactions (Cambridge, England : 2003)
|April 18, 2012
Summary
Methyl triflate (MeOTf) alkylates titanium imido complexes, forming methylamido titanium derivatives. These compounds rearrange to yield methylimido titanium complexes, offering new synthetic pathways.
Area of Science:
- Organometallic Chemistry
- Titanium Chemistry
- Ligand Modification
Background:
- Titanium imido complexes are versatile building blocks in inorganic synthesis.
- Understanding ligand reactivity is crucial for controlling complex structures and properties.
- Alkylation reactions offer a route to functionalize metal-nitrogen bonds.
Purpose of the Study:
- To investigate the alkylation of a specific titanium imido cluster with methyl triflate.
- To characterize the resulting methylamido and methylimido titanium complexes.
- To elucidate the rearrangement pathway from methylamido to methylimido species.
Main Methods:
- Reaction of [{Ti(η(5)-C(5)Me(5))(μ-NH)}(3)(μ(3)-N)] with methyl triflate (MeOTf).
- Isolation and characterization of the intermediate methylamido complex.
- Observation and characterization of the subsequent rearrangement to the methylimido complex.
Main Results:
- Alkylation occurred selectively at the imido ligands, yielding a methylamido derivative.
- The methylamido complex readily underwent rearrangement.
- A novel methylimido titanium complex with a unique ligand arrangement was formed.
Conclusions:
- Methyl triflate is an effective alkylating agent for titanium imido ligands.
- A facile rearrangement pathway from methylamido to methylimido titanium complexes exists.
- This study expands the synthetic repertoire for titanium-nitrogen cluster compounds.
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