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Title: Multiple N–H and C–H Hydrogen Atom Abstractions Through Coordination-Induced Bond Weakening at Fe-Amine Complexes

Abstract

We report the use of the reported Fe-phthalocyanine complex, PcFe (1; Pc = 1,4,8,11,15,18,22,25-octaethoxy-phthalocyanine), to generate PcFe–amine complexes 1-(NH3)2, 1-(MeNH2)2, and 1-(Me2NH)2. Treatment of 1 or 1-(NH3)2 to an excess of the stable aryloxide radical, 2,4,6-tritert-butylphenoxyl radical (tBuArO•), under NH3 resulted in catalytic H atom abstraction (HAA) and C–N coupling to generate the product 4-amino-2,4,6-tritert-butylcyclohexa-2,5-dien-1-one (2) and tBuArOH. Exposing 1-(NH3)2 to an excess of the trityl (CPh3) variant, 2,6-di-tert-butyl-4-tritylphenoxyl radical (TrArO•), under NH3 did not lead to catalytic ammonia oxidation as previously reported in a related Ru-porphyrin complex. However, pronounced coordination-induced bond weakening of both α N–H and β C–H in the alkylamine congeners, 1-(MeNH2)2 and 1-(Me2NH)2, led to multiple HAA events yielding the unsaturated cyanide complex, 1-(MeNH2)(CN), and imine complex, 1-(MeN=CH2)2, respectively. Subsequent C–N bond formation was also observed in the latter upon addition of a coordinating ligand. Detailed computational studies support an alternating mechanism involving sequential N–H and C–H HAA to generate these unsaturated products.

Authors:
 [1]; ORCiD logo [2];  [1]; ORCiD logo [1]
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  1. Univ. of California, Santa Barbara, CA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Center for Molecular Electrocatalysis
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1804674
Report Number(s):
PNNL-SA-161871
Journal ID: ISSN 0020-1669
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 60; Journal Issue: 11; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Free energy; Amines; Bond cleavage; Chemical calculations; Nuclear magnetic resonance spectroscopy

Citation Formats

Wang, Zongheng, Johnson, Samantha I., Wu, Guang, and Ménard, Gabriel. Multiple N–H and C–H Hydrogen Atom Abstractions Through Coordination-Induced Bond Weakening at Fe-Amine Complexes. United States: N. p., 2021. Web. doi:10.1021/acs.inorgchem.1c00923.
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Wang, Zongheng, Johnson, Samantha I., Wu, Guang, & Ménard, Gabriel. Multiple N–H and C–H Hydrogen Atom Abstractions Through Coordination-Induced Bond Weakening at Fe-Amine Complexes. United States. https://doi.org/10.1021/acs.inorgchem.1c00923
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Wang, Zongheng, Johnson, Samantha I., Wu, Guang, and Ménard, Gabriel. Wed . "Multiple N–H and C–H Hydrogen Atom Abstractions Through Coordination-Induced Bond Weakening at Fe-Amine Complexes". United States. https://doi.org/10.1021/acs.inorgchem.1c00923. https://www.osti.gov/servlets/purl/1804674.
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@article{osti_1804674,
title = {Multiple N–H and C–H Hydrogen Atom Abstractions Through Coordination-Induced Bond Weakening at Fe-Amine Complexes},
author = {Wang, Zongheng and Johnson, Samantha I. and Wu, Guang and Ménard, Gabriel},
abstractNote = {We report the use of the reported Fe-phthalocyanine complex, PcFe (1; Pc = 1,4,8,11,15,18,22,25-octaethoxy-phthalocyanine), to generate PcFe–amine complexes 1-(NH3)2, 1-(MeNH2)2, and 1-(Me2NH)2. Treatment of 1 or 1-(NH3)2 to an excess of the stable aryloxide radical, 2,4,6-tritert-butylphenoxyl radical (tBuArO•), under NH3 resulted in catalytic H atom abstraction (HAA) and C–N coupling to generate the product 4-amino-2,4,6-tritert-butylcyclohexa-2,5-dien-1-one (2) and tBuArOH. Exposing 1-(NH3)2 to an excess of the trityl (CPh3) variant, 2,6-di-tert-butyl-4-tritylphenoxyl radical (TrArO•), under NH3 did not lead to catalytic ammonia oxidation as previously reported in a related Ru-porphyrin complex. However, pronounced coordination-induced bond weakening of both α N–H and β C–H in the alkylamine congeners, 1-(MeNH2)2 and 1-(Me2NH)2, led to multiple HAA events yielding the unsaturated cyanide complex, 1-(MeNH2)(CN), and imine complex, 1-(MeN=CH2)2, respectively. Subsequent C–N bond formation was also observed in the latter upon addition of a coordinating ligand. Detailed computational studies support an alternating mechanism involving sequential N–H and C–H HAA to generate these unsaturated products.},
doi = {10.1021/acs.inorgchem.1c00923},
journal = {Inorganic Chemistry},
number = 11,
volume = 60,
place = {United States},
year = {Wed May 19 00:00:00 EDT 2021},
month = {Wed May 19 00:00:00 EDT 2021}
}
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