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Title: 1,2-Addition of Formic or Oxalic Acid to N{CH2CH2(PiPr2)}2 -Supported Mn(I) Dicarbonyl Complexes and the Manganese-Mediated Decomposition of Formic Acid

Abstract

(PNHP)Mn(CO)2 (I) carboxylate complexes (PNHP = HN{CH2CH2(PiPr2)}2) were prepared in this study via 1,2-addition of either formic or oxalic acid to (PNP)Mn(CO)2 (PNP = the deprotonated, amide form of the ligand –N{CH2CH2(PiPr2)}2). The structural and spectral properties of these complexes were compared. The manganese formate complex was found to be dimeric in the solid state and monomeric in solution. Half an equivalent of oxalic acid was employed to form the bridging oxalate dimanganese complex. The catalytic competencies of the carboxylate complexes were assessed, and the formate complex was found to decompose formic acid catalytically. Both dehydrogenation and dehydration pathways were active as assessed by the presence of H2, CO2, and H2O. Lastly, the addition of LiBF4 exhibited a strong inhibitory effect on the catalysis.

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1483496
Report Number(s):
LA-UR-16-22530
Journal ID: ISSN 0276-7333
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Accepted Manuscript
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 35; Journal Issue: 12; Journal ID: ISSN 0276-7333
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Tondreau, Aaron M., and Boncella, James M. 1,2-Addition of Formic or Oxalic Acid to –N{CH2CH2(PiPr2)}2 -Supported Mn(I) Dicarbonyl Complexes and the Manganese-Mediated Decomposition of Formic Acid. United States: N. p., 2016. Web. doi:10.1021/acs.organomet.6b00274.
Tondreau, Aaron M., & Boncella, James M. 1,2-Addition of Formic or Oxalic Acid to –N{CH2CH2(PiPr2)}2 -Supported Mn(I) Dicarbonyl Complexes and the Manganese-Mediated Decomposition of Formic Acid. United States. https://doi.org/10.1021/acs.organomet.6b00274
Tondreau, Aaron M., and Boncella, James M. Tue . "1,2-Addition of Formic or Oxalic Acid to –N{CH2CH2(PiPr2)}2 -Supported Mn(I) Dicarbonyl Complexes and the Manganese-Mediated Decomposition of Formic Acid". United States. https://doi.org/10.1021/acs.organomet.6b00274. https://www.osti.gov/servlets/purl/1483496.
@article{osti_1483496,
title = {1,2-Addition of Formic or Oxalic Acid to –N{CH2CH2(PiPr2)}2 -Supported Mn(I) Dicarbonyl Complexes and the Manganese-Mediated Decomposition of Formic Acid},
author = {Tondreau, Aaron M. and Boncella, James M.},
abstractNote = {(PNHP)Mn(CO)2 (I) carboxylate complexes (PNHP = HN{CH2CH2(PiPr2)}2) were prepared in this study via 1,2-addition of either formic or oxalic acid to (PNP)Mn(CO)2 (PNP = the deprotonated, amide form of the ligand –N{CH2CH2(PiPr2)}2). The structural and spectral properties of these complexes were compared. The manganese formate complex was found to be dimeric in the solid state and monomeric in solution. Half an equivalent of oxalic acid was employed to form the bridging oxalate dimanganese complex. The catalytic competencies of the carboxylate complexes were assessed, and the formate complex was found to decompose formic acid catalytically. Both dehydrogenation and dehydration pathways were active as assessed by the presence of H2, CO2, and H2O. Lastly, the addition of LiBF4 exhibited a strong inhibitory effect on the catalysis.},
doi = {10.1021/acs.organomet.6b00274},
journal = {Organometallics},
number = 12,
volume = 35,
place = {United States},
year = {2016},
month = {6}
}

Journal Article:
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Cited by: 38 works
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Figures / Tables:

Figure 1 Figure 1: Comparison of isoelectronic metal complexes of Fe(II) and Mn(I).

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