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Title: Synthesis and Protonation Studies of Molybdenum(0) Bis(dinitrogen) Complexes Supported by Diphosphine Ligands Containing Pendant Amines

A series of molybdenum bis(dinitrogen) complexes of the formula trans-Mo(N2)2(PEtNRPEt)2 (PEtNRPEt = Et2PCH2N(R)CH2Et2; R = phenyl (1), 2,6-difluorobenzyl (2), 3,5-difluorobenzyl (3), CH2CH2NMe2 (4), CH2-o-Py (5)) have been synthesized and characterized by NMR and IR spectroscopy, and X-ray crystallography. Protonation studies with stoichiometric amounts of triflic acid (HOTf) were performed and the the protonated products were characterized by NMR and in situ IR spectroscopic methods. Protonolysis experiments with excess triflic acid were conducted to test for the formation of ammonia from reduction of the dinitrogen ligands. 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 Office of Science, Office of Basic Energy Sciences. S.L. was supported by the DOE Office of Science, Early Career Research Program through the Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for DOE.
Authors:
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Publication Date:
OSTI Identifier:
1191800
Report Number(s):
PNNL-SA-101420
KC0307010
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Zeitschrift fuer Anorganische und Allgemeine Chemie, 641(1):105-117
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
molybdenum; dinitrogen; ammonia; nitrogenase; catalyst