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Published on: May 13, 2013
Nitrogen fixation to cyanide at a molybdenum center
John J Curley1, Anthony F Cozzolino, Christopher C Cummins
1Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139-4307, USA.
Dalton Transactions (Cambridge, England : 2003)
|February 5, 2011
Summary
Researchers developed a new method for synthesizing molybdenum nitride complexes. This study details the methoxymethylation of a nitride precursor, leading to imido and methoxyketimide complexes, and ultimately a terminal cyanide complex.
Area of Science:
- Organometallic Chemistry
- Molybdenum Chemistry
- Nitrile and Imide Synthesis
Background:
- Molybdenum nitride complexes are of interest due to their unique reactivity.
- Developing efficient synthetic routes to functionalized molybdenum imido and cyanide complexes is crucial for exploring their catalytic potential.
Purpose of the Study:
- To investigate the methoxymethylation of N(2)-derived nitride molybdenum complexes.
- To synthesize novel imido, methoxyketimide, and terminal cyanide complexes of molybdenum.
Main Methods:
- Methoxymethylation of the N(2)-derived nitride NMo(N[(t)Bu]Ar)(3) using a triflate salt.
- Reaction of the imido cation with lithium bis(trimethylsilyl)amide to form a methoxyketimide complex.
- Conversion of the methoxyketimide to a terminal cyanide complex using tin(II) chloride and N,N-dimethyl(trimethylsilyl)amine.
Main Results:
- The imido cation [MeOCH(2)NMo(N[(t)Bu]Ar)(3)](+) was synthesized in 88% yield.
- The blue methoxyketimide complex MeO(H)CNMo(N[(t)Bu]Ar)(3) was obtained in 95% yield.
- The terminal cyanide complex NCMo(N[(t)Bu]Ar)(3) was successfully synthesized in 51% yield and characterized by X-ray diffraction.
Conclusions:
- A facile synthetic pathway to functionalized molybdenum imido and cyanide complexes has been established.
- The study provides new insights into the reactivity of molybdenum nitride precursors.
- The characterized terminal cyanide complex offers opportunities for further investigation in catalysis and materials science.
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