Catalytic Reduction of Dinitrogen to Ammonia by Molybdenum: Theory versus Experiment

摘要

Molybdenum complexes that contain the triamidoamine ligand [(RNCH2CH2)3N]~(3-) (R =3,5-(2,4,6-iPr3C6H2)2C6H3) catalyze the reduction of dinitrogen to ammonia at 22°C and 1 atm with protons from 2,6-dimethylpyridinium and electrons from deca-methylchromocene. 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 [(HIPTNCH2CH2)3N]Mo species (HIPT=hexa-isopropylterphenyl=3,5-(2,4,6-iPr3C6H2)2C6H3), 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.