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Title: Manganese Mediated Formic Acid Dehydrogenation

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 tBuPNNOP ( tBuPNNOP=2,6–(di– tert–butylphosphinito)(di– tert–butylphosphinamine)pyridine) (1) and the catalyst is readily prepared with MnBrCO 5 to form [( tBuPNNOP)Mn(CO) 2][Br] (2). Dehydrohalogenation of 2 generated the neutral five coordinate complex ( tBuPNNOP)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, tBuPONOP ( tBuPONOP=2,6–bis(di– tert–butylphosphinito)pyridine) or tBuPNNNP ( tBuPNNNP=2,6–bis (di– tert–butylphosphinamine)pyridine), coordination complexes of Mn were synthesized, respectively affording [( tBuPONOP)Mn(CO) 2][Br] (4) and [( tBuPNNNP)Mn(CO) 2][Br] (5). In conclusion, 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]
  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
OSTI Identifier:
1532714
Report Number(s):
LA-UR-18-31831
Journal ID: ISSN 0947-6539
Grant/Contract Number:  
89233218CNA000001
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:
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.
Anderson, Nickolas H., Boncella, James M., & Tondreau, Aaron Maurice. Manganese Mediated Formic Acid Dehydrogenation. United States. doi:10.1002/chem.201901177.
Anderson, Nickolas H., Boncella, James M., and Tondreau, Aaron Maurice. Wed . "Manganese Mediated Formic Acid Dehydrogenation". United States. doi:10.1002/chem.201901177.
@article{osti_1532714,
title = {Manganese Mediated Formic Acid Dehydrogenation},
author = {Anderson, Nickolas H. and Boncella, James M. and Tondreau, Aaron Maurice},
abstractNote = {A robust and rapid manganese formic acid (FA) dehydrogenation catalyst is reported. The manganese is supported by the recently developed, hybrid backbone chelate ligand tBuPNNOP (tBuPNNOP=2,6–(di–tert–butylphosphinito)(di–tert–butylphosphinamine)pyridine) (1) and the catalyst is readily prepared with MnBrCO5 to form [(tBuPNNOP)Mn(CO)2][Br] (2). Dehydrohalogenation of 2 generated the neutral five coordinate complex (tBuPNNOP)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, tBuPONOP (tBuPONOP=2,6–bis(di–tert–butylphosphinito)pyridine) or tBuPNNNP (tBuPNNNP=2,6–bis (di–tert–butylphosphinamine)pyridine), coordination complexes of Mn were synthesized, respectively affording [(tBuPONOP)Mn(CO)2][Br] (4) and [(tBuPNNNP)Mn(CO)2][Br] (5). In conclusion, 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 = {2019},
month = {5}
}

Journal Article:
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This content will become publicly available on May 8, 2020
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