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Reduction of Dinitrogen to Ammonia Catalyzed by Molybdenum Diamido Complexes
Lasantha A Wickramasinghe1, Takaya Ogawa1, Richard R Schrock1
1Department of Chemistry 6-331, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
Abstract:
[Ar2N3]Mo(N)(O-t-Bu), which contains the conformationally rigid pyridine-based diamido ligand, [2,6-(ArNCH2)2NC5H3]2- (Ar = 2,6-diisopropylphenyl), can be prepared from H2[Ar2N3], butyllithium, and (t-BuO)3Mo(N). [Ar2N3]Mo(N)(O-t-Bu) serves as a catalyst or precursor for the catalytic reduction of molecular nitrogen to ammonia in diethyl ether between -78 and 22 °C in a batchwise manner with CoCp*2 as the electron source and Ph2NH2OTf as the proton source. Up to ∼10 equiv of ammonia can be formed per Mo with a maximum efficiency in electrons of ∼43%.
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