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Utilization of Stop-flow Micro-tubing Reactors for the Development of Organic Transformations
Published on: January 4, 2018
A cycle for organic nitrile synthesis via dinitrogen cleavage
John J Curley1, Emma L Sceats, Christopher C Cummins
1Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139, USA.
Journal of the American Chemical Society
|October 26, 2006
Summary
This study presents a novel synthetic route for derivatizing nitrogen gas (N2) using molybdenum nitride complexes. New strategies enable the functionalization of hindered nitrides and nitrile extrusion from ketimides.
Area of Science:
- Organometallic Chemistry
- Inorganic Chemistry
- Synthetic Chemistry
Background:
- Nitrogen gas (N2) fixation remains a significant challenge in chemistry.
- Sterically hindered metal nitrides offer unique reactivity for N2 functionalization.
- Developing efficient catalytic cycles for N2 derivatization is crucial.
Purpose of the Study:
- To establish a new synthetic pathway for derivatizing N2.
- To explore the functionalization of sterically hindered nitrides.
- To investigate nitrile extrusion from d2 ketimides.
Main Methods:
- Reaction of N2 with Mo(N[t-Bu]Ar)3 in the presence of NaH.
- Lewis acid-mediated acylation of the nitride complex.
- Reduction and silylation to form molybdenum ketimides.
- Nitrile extrusion using SnCl2 or ZnCl2, followed by reduction to regenerate the starting molybdenum complex.
Main Results:
- Successful synthesis of NMo(N[t-Bu]Ar)3 from N2.
- Formation of acyl imido and molybdenum ketimide intermediates.
- Efficient generation of ClMo(N[t-Bu]Ar)3 and organic nitriles (RCN).
- Regeneration of the starting molybdenum complex, completing a catalytic cycle.
Conclusions:
- A new synthetic cycle for N2 derivatization has been developed.
- Sterically hindered nitrides can be effectively functionalized.
- Nitrile extrusion from d2 ketimides provides a viable synthetic route.
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