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Title: Manganese Mediated Formic Acid Dehydrogenation

Abstract

Abstract A robust and rapid manganese formic acid (FA) dehydrogenation catalyst is reported. The manganese is supported by the recently developed, hybrid backbone chelate ligand t Bu PNNOP ( t Bu PNNOP=2,6‐(di‐ tert ‐butylphosphinito)(di‐ tert ‐butylphosphinamine)pyridine) ( 1 ) and the catalyst is readily prepared with MnBrCO 5 to form [( t Bu PNNOP)Mn(CO) 2 ][Br] ( 2 ). Dehydrohalogenation of 2 generated the neutral five coordinate complex ( t Bu PNNOP)Mn(CO) 2 ( 3 ). Dehydrogenation of FA by 2 and 3 was found to be highly efficient, exhibiting turnover frequencies (TOFs) exceeding 8500 h −1 , rivaling many noble metal systems. The parent chelate, t Bu PONOP ( t Bu PONOP=2,6‐bis(di‐ tert ‐butylphosphinito)pyridine) or t Bu PNNNP ( t Bu PNNNP=2,6‐bis (di‐ tert ‐butylphosphinamine)pyridine), coordination complexes of Mn were synthesized, respectively affording [( t Bu PONOP)Mn(CO) 2 ][Br] ( 4 ) and [( t Bu PNNNP)Mn(CO) 2 ][Br] ( 5 ). FA dehydrogenation with the hybrid‐ligand supported 2 exhibits superior catalysis to 4 and 5 .

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1532714
Alternate Identifier(s):
OSTI ID: 1548850
Report Number(s):
LA-UR-18-31831
Journal ID: ISSN 0947-6539
Grant/Contract Number:  
89233218CNA000001; Science Campaign 5
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Name: Chemistry - A European Journal; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis; dehydrogenation; formic acid; manganese; PNNOP

Citation Formats

Anderson, Nickolas H., Boncella, James M., and Tondreau, Aaron Maurice. Manganese Mediated Formic Acid Dehydrogenation. United States: N. p., 2019. Web. doi:10.1002/chem.201901177.
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Anderson, Nickolas H., Boncella, James M., & Tondreau, Aaron Maurice. Manganese Mediated Formic Acid Dehydrogenation. United States. https://doi.org/10.1002/chem.201901177
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Anderson, Nickolas H., Boncella, James M., and Tondreau, Aaron Maurice. Wed . "Manganese Mediated Formic Acid Dehydrogenation". United States. https://doi.org/10.1002/chem.201901177. https://www.osti.gov/servlets/purl/1532714.
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@article{osti_1532714,
title = {Manganese Mediated Formic Acid Dehydrogenation},
author = {Anderson, Nickolas H. and Boncella, James M. and Tondreau, Aaron Maurice},
abstractNote = {Abstract A robust and rapid manganese formic acid (FA) dehydrogenation catalyst is reported. The manganese is supported by the recently developed, hybrid backbone chelate ligand t Bu PNNOP ( t Bu PNNOP=2,6‐(di‐ tert ‐butylphosphinito)(di‐ tert ‐butylphosphinamine)pyridine) ( 1 ) and the catalyst is readily prepared with MnBrCO 5 to form [( t Bu PNNOP)Mn(CO) 2 ][Br] ( 2 ). Dehydrohalogenation of 2 generated the neutral five coordinate complex ( t Bu PNNOP)Mn(CO) 2 ( 3 ). Dehydrogenation of FA by 2 and 3 was found to be highly efficient, exhibiting turnover frequencies (TOFs) exceeding 8500 h −1 , rivaling many noble metal systems. The parent chelate, t Bu PONOP ( t Bu PONOP=2,6‐bis(di‐ tert ‐butylphosphinito)pyridine) or t Bu PNNNP ( t Bu PNNNP=2,6‐bis (di‐ tert ‐butylphosphinamine)pyridine), coordination complexes of Mn were synthesized, respectively affording [( t Bu PONOP)Mn(CO) 2 ][Br] ( 4 ) and [( t Bu PNNNP)Mn(CO) 2 ][Br] ( 5 ). FA dehydrogenation with the hybrid‐ligand supported 2 exhibits superior catalysis to 4 and 5 .},
doi = {10.1002/chem.201901177},
journal = {Chemistry - A European Journal},
number = ,
volume = ,
place = {United States},
year = {Wed May 08 00:00:00 EDT 2019},
month = {Wed May 08 00:00:00 EDT 2019}
}
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