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Title: Exploring the role of pendant amines in transition metal complexes for the reduction of N2 to hydrazine and ammonia

Abstract

This review examines the synthesis and acid reactivity of transition metal dinitrogen complexes bearing diphosphine ligands containing pendant amine groups in the second coordination sphere. This manuscript is a review of the work performed in the Center for Molecular Electrocatalysis. This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy (U.S. DOE), Office of Science, Office of Basic Energy Sciences. EPR studies on Fe were performed using EMSL, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL. Computational resources were provided by the National Energy Research Scientific Computing Center (NERSC) at Lawrence Berkeley National Laboratory. Pacific Northwest National Laboratory is operated by Battelle for the U.S. DOE.

Authors:
; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1343171
Report Number(s):
PNNL-SA-117030
Journal ID: ISSN 0010-8545; 47453; KC0307010
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Coordination Chemistry Reviews; Journal Volume: 334
Country of Publication:
United States
Language:
English
Subject:
dinitrogen; ammonia; hydrazine; phosphines; pendant amine; chromium; molybdenum; tungsten; iron; vanadium; Environmental Molecular Sciences Laboratory

Citation Formats

Bhattacharya, Papri, Prokopchuk, Demyan E., and Mock, Michael T.. Exploring the role of pendant amines in transition metal complexes for the reduction of N2 to hydrazine and ammonia. United States: N. p., 2017. Web. doi:10.1016/j.ccr.2016.07.005.
Bhattacharya, Papri, Prokopchuk, Demyan E., & Mock, Michael T.. Exploring the role of pendant amines in transition metal complexes for the reduction of N2 to hydrazine and ammonia. United States. doi:10.1016/j.ccr.2016.07.005.
Bhattacharya, Papri, Prokopchuk, Demyan E., and Mock, Michael T.. Wed . "Exploring the role of pendant amines in transition metal complexes for the reduction of N2 to hydrazine and ammonia". United States. doi:10.1016/j.ccr.2016.07.005.
@article{osti_1343171,
title = {Exploring the role of pendant amines in transition metal complexes for the reduction of N2 to hydrazine and ammonia},
author = {Bhattacharya, Papri and Prokopchuk, Demyan E. and Mock, Michael T.},
abstractNote = {This review examines the synthesis and acid reactivity of transition metal dinitrogen complexes bearing diphosphine ligands containing pendant amine groups in the second coordination sphere. This manuscript is a review of the work performed in the Center for Molecular Electrocatalysis. This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy (U.S. DOE), Office of Science, Office of Basic Energy Sciences. EPR studies on Fe were performed using EMSL, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL. Computational resources were provided by the National Energy Research Scientific Computing Center (NERSC) at Lawrence Berkeley National Laboratory. Pacific Northwest National Laboratory is operated by Battelle for the U.S. DOE.},
doi = {10.1016/j.ccr.2016.07.005},
journal = {Coordination Chemistry Reviews},
number = ,
volume = 334,
place = {United States},
year = {Wed Mar 01 00:00:00 EST 2017},
month = {Wed Mar 01 00:00:00 EST 2017}
}
  • Cited by 6
  • Nickel(II) bis(diphosphine) complexes that contain positioned bases in the second coordination sphere have been found to catalyze the reduction of O2 with H2 to selectively form water. The complexes also serve as electrocatalysts for the reduction of O2 with the addition of a weak acid. In contrast, a closely related nickel diphosphine complex without the positioned bases is catalytically inactive for O2 reduction. These results indicate that pendant bases in synthetic catalysts for O2 reduction can play a similar role to proton relays in enzymes, and that such relays should be considered in the design of catalysts for multi-electron andmore » multi-proton reactions. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less
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