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

作者：Richard R. Schrock · 发表于：Angewandte Chemie International Edition · 年份：2008 · DOI：10.1002/anie.200705246 · 被引用次数：353 · 研究领域：Ammonia Synthesis and Nitrogen Reduction、Metal-Organic Frameworks: Synthesis and Applications、Carbon dioxide utilization in catalysis

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.