skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

We report that [Ar 2N 3]Mo(N)(O-t-Bu), which contains the conformationally rigid pyridine-based diamido ligand, [2,6-(ArNCH 2) 2NC 5H 3] 2– (Ar = 2,6-diisopropylphenyl), can be prepared from H 2[Ar 2N 3], 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 Ph 2NH 2OTf 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:
Journal Article: 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. https://doi.org/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. https://doi.org/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},
url = {https://www.osti.gov/biblio/1535022}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 27,
volume = 139,
place = {United States},
year = {2017},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 63 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

CCDC 1564767: Experimental Crystal Structure Determination
dataset, January 2017


CCDC 1564768: Experimental Crystal Structure Determination
dataset, January 2017


CCDC 1564766: Experimental Crystal Structure Determination
dataset, January 2017


Catalytic Reduction of Molecular Dinitrogen to Ammonia and Hydrazine Using Vanadium Complexes
journal, April 2018


Influence of a Metal Substrate on Small-Molecule Activation Mediated by a Surface-Adsorbed Complex
journal, June 2018


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


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


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


Tetrahedral iron featuring an appended Lewis acid: distinct pathways for the reduction of hydroxylamine and hydrazine
journal, January 2019


A reactive coordinatively saturated Mo( iii ) complex: exploiting the hemi-lability of tris( tert -butoxy)silanolate ligands
journal, January 2019


Catalysts for nitrogen reduction to ammonia
journal, July 2018


Flexible N-Donor Ligands Direct the Structural Characteristics of CoII Complexes: Syntheses, Structures, and Magnetic Properties
journal, January 2019


Catalytic Reduction of Molecular Dinitrogen to Ammonia and Hydrazine Using Vanadium Complexes
journal, April 2018


Influence of a Metal Substrate on Small-Molecule Activation Mediated by a Surface-Adsorbed Complex
journal, June 2018


Catalysts for nitrogen reduction to ammonia
journal, July 2018


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


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


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


Tetrahedral iron featuring an appended Lewis acid: distinct pathways for the reduction of hydroxylamine and hydrazine
journal, January 2019


A reactive coordinatively saturated Mo( iii ) complex: exploiting the hemi-lability of tris( tert -butoxy)silanolate ligands
journal, January 2019


Flexible N-Donor Ligands Direct the Structural Characteristics of CoII Complexes: Syntheses, Structures, and Magnetic Properties
journal, January 2019


Catalytic Reduction of Molecular Dinitrogen to Ammonia and Hydrazine Using Vanadium Complexes
journal, April 2018


Dinitrogen‐Molybdenum Complex Induces Dinitrogen Cleavage by One‐Electron Oxidation
journal, July 2019


Dinitrogen‐Molybdenum Complex Induces Dinitrogen Cleavage by One‐Electron Oxidation
journal, August 2019


Synthesis and Reactivity of Cationic Boron Complexes Distorted by Pyridine‐based Pincer Ligands: Isolation of a Photochemical Hofmann–Martius‐type Intermediate
journal, February 2020


Nitrogen Fixation Catalyzed by Transition Metal Complexes: Recent Developments: Nitrogen Fixation Catalyzed by Transition Metal Complexes: Recent Developments
journal, February 2018


Electrochemical Reduction of N 2 to NH 3 Using a Co‐Atom Stabilized on Defective N‐Doped Graphene: A Computational Study
journal, November 2019


Electrochemical N 2 fixation to NH 3 under ambient conditions: Mo 2 N nanorod as a highly efficient and selective catalyst
journal, January 2018


Synthesis and reactivity of asymmetric Cr( i ) dinitrogen complexes supported by cyclopentadienyl–phosphine ligands
journal, January 2019