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Title: Protonation Studies of a Mono-Dinitrogen Complex of Chromium Supported by a 12-Membered Phosphorus Macrocycle Containing Pendant Amines

Journal Article · · Inorganic Chemistry
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  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division, Center for Molecular Electrocatalysis
  2. Villanova Univ. , PA (United States). Dept. of Chemistry
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The first example of a mono-dinitrogen Cr0 complex, Cr(N2)(dmpe)(PPh3NBn3), 2(N2), (PPh3NBn3 = 1,5,9-tribenzyl-3,7,11-triphenyl-1,5,9-triaza-3,7,11-triphosphacyclododecane; dmpe = 1,2-bis(dimethylphosphino)ethane) containing a pentaphosphine coordination environment is described. 2(N2) is supported by a unique facially coordinating 12-membered phosphorus macrocycle containing pendant amine groups in the second coordination sphere. Treatment of 2(N2) at -78 °C with 1 equiv of [H(OEt2)2][B(C6F5)4] results in protonation of the metal center, generating the 7-coordinate Cr(II)-N2 hydride complex, [Cr(H)(N2)(dmpe)(PPh3NBn3)][B(C6F5)4], [2(H)(N2)]+. Treatment of 2(15N2) with excess triflic acid at -50 °C afforded a trace amount of 15NH4+ from the reduction of the coordinated 15N2 ligand (electrons originate from Cr). Augmenting the acid reactivity studies, electronic structure calculations evaluated the pKa values of three sites of 2(N2) (metal center, pendant amine, and N2 ligand) to elucidate possible Cr-NxHy intermediates involved in the N2 reduction pathways from the protonation of 2(N2). This research 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. Computational resources 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. Department of Energy.

Research Organization:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Center for Molecular Electrocatalysis (CME); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Contributing Organization:
Energy Frontier Research Centers (EFRC) (United States)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1386037
Alternate ID(s):
OSTI ID: 1757944
Report Number(s):
PNNL-SA-108000
Journal Information:
Inorganic Chemistry, Vol. 54, Issue 10; Related Information: CME partners with Pacific Northwest National Laboratory (lead); University of Illinois, Urbana-Champaign; Pennsylvania State University; University of Washington; University of Wyoming; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 20 works
Citation information provided by
Web of Science

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Cited By (6)

Putting chromium on the map for N 2 reduction: production of hydrazine and ammonia. A study of cis-M(N 2 ) 2 (M = Cr, Mo, W) bis(diphosphine) complexes journal January 2016
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
Synthesis and Reactivity of Iron- and Cobalt-Dinitrogen Complexes Bearing PSiP-Type Pincer Ligands toward Nitrogen Fixation: Synthesis and Reactivity of Iron- and Cobalt-Dinitrogen Complexes Bearing PSiP-Type Pincer Ligands toward Nitrogen Fixation journal July 2017
Direct Transformation of Molecular Dinitrogen into Ammonia Catalyzed by Cobalt Dinitrogen Complexes Bearing Anionic PNP Pincer Ligands journal August 2016
Direct Transformation of Molecular Dinitrogen into Ammonia Catalyzed by Cobalt Dinitrogen Complexes Bearing Anionic PNP Pincer Ligands journal August 2016
Synthesis and Reactivity of Iron- and Cobalt-Dinitrogen Complexes Bearing PSiP-Type Pincer Ligands toward Nitrogen Fixation journal July 2017

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalysis (homogeneous)
catalysis (heterogeneous)
solar (fuels)
bio-inspired
energy storage (including batteries and capacitors)
hydrogen and fuel cells
charge transport
materials and chemistry by design
synthesis (novel materials)
Chromium
dinitrogen
ammonia
phosphines
pendant amines