Synthesis of diamidopyrrolyl molybdenum complexes relevant to reduction of dinitrogen to ammonia

A potentially useful trianionic ligand for the reduction of dinitrogen catalytically by molybdenum complexes is one in which one of the arms in a [(RNCH(2)CH(2))(3)N](3-) ligand is replaced by a 2-mesitylpyrrolyl-alpha-methyl arm, that is, [(RNCH(2)CH(2))(2)NCH(2)(2-MesitylPyrrolyl)](3-) (R = C(6)F(5), 3,5-Me(2)C(6)H(3), or 3,5-t-Bu(2)C(6)H(3)). Compounds have been prepared that contain the ligand in which R = C(6)F(5) ([C(6)F(5)N)(2)Pyr](3-)); they include [(C(6)F(5)N)(2)Pyr]Mo(NMe(2)), [(C(6)F(5)N)(2)Pyr]MoCl, [(C(6)F(5)N)(2)Pyr]MoOTf, and [(C(6)F(5)N)(2)Pyr]MoN. Compounds that contain the ligand in which R = 3,5-t-Bu(2)C(6)H(3) ([Ar(t-Bu)N)(2)Pyr](3-)) include {[(Ar(t-Bu)N)(2)Pyr]Mo(N(2))}Na(15-crown-5), {[(Ar(t-Bu)N)(2)Pyr]Mo(N(2))}[NBu(4)], [(Ar(t-Bu)N)(2)Pyr]Mo(N(2)) (nu(NN) = 2012 cm(-1) in C(6)D(6)), {[(Ar(t-Bu)N)(2)Pyr]Mo(NH(3))}BPh(4), and [(Ar(t-Bu)N)(2)Pyr]Mo(CO). X-ray studies are reported for [(C(6)F(5)N)(2)Pyr]Mo(NMe(2)), [(C(6)F(5)N)(2)Pyr]MoCl, and [(Ar(t-Bu)N)(2)Pyr]MoN. The [(Ar(t-Bu)N)(2)Pyr]Mo(N(2))(0/-) reversible couple is found at -1.96 V (in PhF versus Cp(2)Fe(+/0)), but the [(Ar(t-Bu)N)(2)Pyr]Mo(N(2))(+/0) couple is irreversible. Reduction of {[(Ar(t-Bu)N)(2)Pyr]Mo(NH(3))}BPh(4) under Ar at approximately -1.68 V at a scan rate of 900 mV/s is not reversible. Ammonia in [(Ar(t-Bu)N)(2)Pyr]Mo(NH(3)) can be substituted for dinitrogen in about 2 h if 10 equiv of BPh(3) are present to trap the ammonia that is released. [(Ar(t-Bu)N)(2)Pyr]Mo-N=NH is a key intermediate in the proposed catalytic reduction of dinitrogen that could not be prepared. Dinitrogen exchange studies in [(Ar(t-Bu)N)(2)Pyr]Mo(N(2)) suggest that steric hindrance by the ligand may be insufficient to protect decomposition of [(Ar(t-Bu)N)(2)Pyr]Mo-N=NH through a variety of pathways. Three attempts to reduce dinitrogen catalytically with [(Ar(t-Bu)N)(2)Pyr]Mo(N) as a "catalyst" yielded an average of 1.02 +/- 0.12 equiv of NH(3).