Catalytic Reduction of Dinitrogen to Ammonia at a Single Molybdenum Center

@article{Yandulov2003CatalyticRO,
  title={Catalytic Reduction of Dinitrogen to Ammonia at a Single Molybdenum Center},
  author={Dmitry V. Yandulov and Richard R. Schrock},
  journal={Science},
  year={2003},
  volume={301},
  pages={76 - 78}
}
Dinitrogen (N2) was reduced to ammonia at room temperature and 1 atmosphere with molybdenum catalysts that contain tetradentate [HIPTN3N]3– triamidoamine ligands {such as [HIPTN3N]Mo(N2), where [HIPTN3N]3– is [{3,5-(2,4,6-i-Pr3C6H2)2C6H3NCH2CH2}3N]3–} in heptane. Slow addition of the proton source [{2,6-lutidinium}{BAr′4}, where Ar′ is 3,5-(CF3)2C6H3]and reductant (decamethyl chromocene) was critical for achieving high efficiency (∼66% in four turnovers). Numerous x-ray studies, along with… Expand
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Density-functional theory (DFT) calculations reveal that the unstable monomeric oxidized MoI species is converted into 2 via the dimeric structure involving a zigzag transition state. Expand
Towards Catalytic Ammonia Oxidation to Dinitrogen: A Synthetic Cycle by Using a Simple Manganese Complex.
TLDR
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Catalytic reduction of dinitrogen to ammonia by molybdenum: theory versus experiment.
  • R. Schrock
  • Chemistry, Medicine
  • Angewandte Chemie
  • 2008
TLDR
Current theoretical findings are compared with experimental findings for each proposed step in the catalytic reaction, including DFT calculations on HIPT species, which contain the actual triamidoamine ligand that is present in catalytic intermediates. Expand
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[HIPTN3N]WCl (WCl) can be synthesized readily by adding H3[HIPTN3N] to WCl4(DME) followed by LiN(SiMe3)2 ([HIPTN3N]3– = [(HIPTNCH2CH2)3N]3– where HIPT = 3,5-(2,4,6-i-Pr3C6H2)2C6H3 =Expand
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A bimetallic molybdenum complex bridged by an activated dinitrogen ligand and supported by phosphine and terpyridine ligands was synthesized and structurally characterized, and its electronic structure was determined using a combination of experimental and density functional theory computational methods. Expand
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The proposed mechanism involves initial adduct formation that facilitates inner-sphere electron transfer to cleave the N-N bond to form a species with bridging nitrides, one of which is transformed by nucleophilic attack of a phosphine donor to generate the observed phosphinimide. Expand
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