Catalytic reduction of dinitrogen to ammonia by molybdenum: theory versus experiment.

Molybdenum complexes that contain the triamidoamine ligand [(RNCH(2)CH(2))(3)N](3-) (R = 3,5-(2,4,6-iPr(3)C(6)H(2))(2)C(6)H(3)) catalyze the reduction of dinitrogen to ammonia at 22 degrees C and 1 atm with protons from 2,6-dimethylpyridinium and electrons from decamethylchromocene. Several theoretical studies have been published that bear on the proposed intermediates in the catalytic dinitrogen reduction reaction and their reaction characteristics, including DFT calculations on [(HIPTNCH(2)CH(2))(3)N]Mo species (HIPT =hexaisopropylterphenyl = 3,5-(2,4,6-iPr(3)C(6)H(2))(2)C(6)H(3)), which contain the actual triamidoamine ligand that is present in catalytic intermediates. Recent theoretical findings are compared with experimental findings for each proposed step in the catalytic reaction.