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Title: Reduction of Dinitrogen to Ammonia Catalyzed by Molybdenum Diamido Complexes

Abstract

We report that [Ar2N3]Mo(N)(O-t-Bu), which contains the conformationally rigid pyridine-based diamido ligand, [2,6-(ArNCH2)2NC5H3]2– (Ar = 2,6-diisopropylphenyl), can be prepared from H2[Ar2N3], butyllithium, and (t-BuO)3Mo(N). [Ar2N3]Mo(N)(O-t-Bu) serves as a catalyst or precursor for the catalytic reduction of molecular nitrogen to ammonia in diethyl ether between -78 and 22 °C in a batchwise manner with CoCp*2 as the electron source and Ph2NH2OTf as the proton source. Up to ~10 equiv of ammonia can be formed per Mo with a maximum efficiency in electrons of ~43%.

Authors:
 [1];  [1]; ORCiD logo [1];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Publication Date:
Research Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1535022
Grant/Contract Number:  
SC0013307
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 27; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wickramasinghe, Lasantha A., Ogawa, Takaya, Schrock, Richard R., and Müller, Peter. Reduction of Dinitrogen to Ammonia Catalyzed by Molybdenum Diamido Complexes. United States: N. p., 2017. Web. doi:10.1021/jacs.7b04800.
Wickramasinghe, Lasantha A., Ogawa, Takaya, Schrock, Richard R., & Müller, Peter. Reduction of Dinitrogen to Ammonia Catalyzed by Molybdenum Diamido Complexes. United States. doi:10.1021/jacs.7b04800.
Wickramasinghe, Lasantha A., Ogawa, Takaya, Schrock, Richard R., and Müller, Peter. Thu . "Reduction of Dinitrogen to Ammonia Catalyzed by Molybdenum Diamido Complexes". United States. doi:10.1021/jacs.7b04800. https://www.osti.gov/servlets/purl/1535022.
@article{osti_1535022,
title = {Reduction of Dinitrogen to Ammonia Catalyzed by Molybdenum Diamido Complexes},
author = {Wickramasinghe, Lasantha A. and Ogawa, Takaya and Schrock, Richard R. and Müller, Peter},
abstractNote = {We report that [Ar2N3]Mo(N)(O-t-Bu), which contains the conformationally rigid pyridine-based diamido ligand, [2,6-(ArNCH2)2NC5H3]2– (Ar = 2,6-diisopropylphenyl), can be prepared from H2[Ar2N3], butyllithium, and (t-BuO)3Mo(N). [Ar2N3]Mo(N)(O-t-Bu) serves as a catalyst or precursor for the catalytic reduction of molecular nitrogen to ammonia in diethyl ether between -78 and 22 °C in a batchwise manner with CoCp*2 as the electron source and Ph2NH2OTf as the proton source. Up to ~10 equiv of ammonia can be formed per Mo with a maximum efficiency in electrons of ~43%.},
doi = {10.1021/jacs.7b04800},
journal = {Journal of the American Chemical Society},
number = 27,
volume = 139,
place = {United States},
year = {2017},
month = {6}
}

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Works referencing / citing this record:

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dataset, January 2017

  • Wickramasinghe, Lasantha A.; Ogawa, Takaya; Schrock, Richard R.
  • Cambridge Crystallographic Data Centre
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CCDC 1564766: Experimental Crystal Structure Determination
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  • Cambridge Crystallographic Data Centre
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Catalytic Reduction of Molecular Dinitrogen to Ammonia and Hydrazine Using Vanadium Complexes
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Influence of a Metal Substrate on Small-Molecule Activation Mediated by a Surface-Adsorbed Complex
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Molybdenum Complexes Supported by PN 3 P Pincer Ligands: Synthesis, Characterization, and Application to Synthetic Nitrogen Fixation : Molybdenum Complexes Supported by PN
journal, December 2018

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Catalysts for nitrogen reduction to ammonia
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journal, January 2018

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Synthesis and reactivity of titanium- and zirconium-dinitrogen complexes bearing anionic pyrrole-based PNP-type pincer ligands
journal, January 2018

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Molybdenum dinitrogen complex supported by a cyclohexane-based triphosphine ligand and dmpm
journal, January 2019

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Effect of substituents on molybdenum triiodide complexes bearing PNP-type pincer ligands toward catalytic nitrogen fixation
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journal, January 2019

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A reactive coordinatively saturated Mo( iii ) complex: exploiting the hemi-lability of tris( tert -butoxy)silanolate ligands
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