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Porphyrin complexes are well-known in O 2 and CO 2 reduction, but their application to N 2 reduction is less developed. Here, we show that oxo and nitrido complexes of molybdenum supported by tetramesitylporphyrin (TMP) are effective precatalysts for catalytic N 2 reduction to ammonia, verified by 15 N 2 labeling studies and other control experiments. Spectroscopic and electrochemical studies illuminate some relevant thermodynamic parameters, including the N–H bond dissociation free energy of (TMP)MoNH (43 ± 2 kcal mol −1 ). We place these results in the context of other work on homogeneous N 2 reduction catalysis.more » « less
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Hasanayn, Faraj ; Holland, Patrick L. ; Goldman, Alan S. ; Miller, Alexander J. M. ( , Journal of the American Chemical Society)
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Lacey, Roy A. ; Wei, Rui ; Jia, J. ; Ajitanand, N. N. ; Alexander, J. M. ; Taranenko, A. ( , Physical Review C)