1253967-26-8Relevant articles and documents
Synthesis of diamidopyrrolyl molybdenum complexes relevant to reduction of dinitrogen to ammonia
Chin,Schrock,Mueller
, p. 7904 - 7916 (2010)
A potentially useful trianionic ligand for the reduction of dinitrogen catalytically by molybdenum complexes is one in which one of the arms in a [(RNCH2CH2)3N]3- ligand is replaced by a 2-mesitylpyrrolyl-α-methyl arm, that is, [(RNCH2CH 2)2NCH2(2-MesitylPyrrolyl)]3- (R = C6F5, 3,5-Me2C6H3, or 3,5-t-Bu2C6H3). Compounds have been prepared that contain the ligand in which R = C6F5 ([C 6F5N)2Pyr]3-); they include [(C 6F5N)2Pyr]Mo(NMe2), [(C 6F5N)2Pyr]MoCl, [(C6F 5N)2Pyr]MoOTf, and [(C6F5N) 2Pyr]MoN. Compounds that contain the ligand in which R = 3,5-t-Bu2C6H3 ([Art-BuN) 2Pyr]3-) include {[(Art-BuN) 2Pyr]Mo(N2)}Na(15-crown-5), {[(Art-BuN) 2Pyr]Mo(N2)}[NBu4], [(Art-BuN) 2Pyr]Mo(N2) (νNN = 2012 cm-1 in C6D6), {[(Art-BuN)2Pyr]Mo(NH 3)}BPh4, and [(Art-BuN)2Pyr]Mo(CO). X-ray studies are reported for [(C6F5N) 2Pyr]Mo(NMe2), [(C6F5N) 2Pyr]MoCl, and [(Art-BuN)2Pyr]MoN. The [(Art-BuN)2Pyr]Mo(N2)0/- reversible couple is found at -1.96 V (in PhF versus Cp2Fe+/0), but the [(Art-BuN)2Pyr]Mo(N2)+/0 couple is irreversible. Reduction of {[(Art-BuN)2Pyr]Mo(NH 3)}BPh4 under Ar at approximately -1.68 V at a scan rate of 900 mV/s is not reversible. Ammonia in [(Art-BuN) 2Pyr]Mo(NH3) can be substituted for dinitrogen in about 2 h if 10 equiv of BPh3 are present to trap the ammonia that is released. [(Art-BuN)2Pyr]Mo-N=NH is a key intermediate in the proposed catalytic reduction of dinitrogen that could not be prepared. Dinitrogen exchange studies in [(Art-BuN)2Pyr]Mo(N 2) suggest that steric hindrance by the ligand may be insufficient to protect decomposition of [(Art-BuN)2Pyr]Mo-N =NH through a variety of pathways. Three attempts to reduce dinitrogen catalytically with [(Art-BuN)2Pyr]Mo(N) as a catalyst yielded an average of 1.02 ± 0.12 equiv of NH3.