TY - JOUR
T1 - Evaluating the impacts of amino acids in the second and outer coordination spheres of Rh-bis(diphosphine) complexes for CO2 hydrogenation
AU - Walsh, Aaron P.
AU - Laureanti, Joseph A.
AU - Katipamula, Sriram
AU - Chambers, Geoffrey M.
AU - Priyadarshani, Nilusha
AU - Lense, Sheri
AU - Bays, J. Timothy
AU - Linehan, John C.
AU - Shaw, Wendy J.
N1 - Funding Information:
This work was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences & Biosciences. A portion of the work (GMC; ligand synthesis) was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. DOE, Office of Science, BES. Pacic Northwest National Laboratory (PNNL) is operated by Battelle for the U.S. DOE. Pacic Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for the DOE by Battelle.
PY - 2019
Y1 - 2019
N2 - To explore the influence of a biologically inspired second and outer coordination sphere on Rh-bis(diphosphine) CO2 hydrogenation catalysts, a series of five complexes were prepared by varying the substituents on the pendant amine in the P(Et)2CH2NRCH2P(Et)2 ligands (PEtNRPEt), where R consists of methyl ester modified amino acids, including three neutral (glycine methyl ester (GlyOMe), leucine methyl ester (LeuOMe), and phenylalanine methyl ester (PheOMe)), one acidic (aspartic acid dimethyl ester (AspOMe)) and one basic (histidine methyl ester (MeHisOMe)) amino acid esters. The turnover frequencies (TOFs) for CO2 hydrogenation for each of these complexes were compared to those of the non-amino acid containing [Rh(depp)2]+ (depp) and [Rh(PEtNMePEt)2]+ (NMe) complexes. Each complex is catalytically active for CO2 hydrogenation to formate under mild conditions in THF. Catalytic activity spanned a factor of four, with the most active species being the NMe catalyst, while the slowest were the GlyOMe and the AspOMe complexes. When compared to a similar set of catalysts with phenyl-substituted phosphorous groups, a clear contribution of the outer coordination sphere is seen for this family of CO2 hydrogenation catalysts.
AB - To explore the influence of a biologically inspired second and outer coordination sphere on Rh-bis(diphosphine) CO2 hydrogenation catalysts, a series of five complexes were prepared by varying the substituents on the pendant amine in the P(Et)2CH2NRCH2P(Et)2 ligands (PEtNRPEt), where R consists of methyl ester modified amino acids, including three neutral (glycine methyl ester (GlyOMe), leucine methyl ester (LeuOMe), and phenylalanine methyl ester (PheOMe)), one acidic (aspartic acid dimethyl ester (AspOMe)) and one basic (histidine methyl ester (MeHisOMe)) amino acid esters. The turnover frequencies (TOFs) for CO2 hydrogenation for each of these complexes were compared to those of the non-amino acid containing [Rh(depp)2]+ (depp) and [Rh(PEtNMePEt)2]+ (NMe) complexes. Each complex is catalytically active for CO2 hydrogenation to formate under mild conditions in THF. Catalytic activity spanned a factor of four, with the most active species being the NMe catalyst, while the slowest were the GlyOMe and the AspOMe complexes. When compared to a similar set of catalysts with phenyl-substituted phosphorous groups, a clear contribution of the outer coordination sphere is seen for this family of CO2 hydrogenation catalysts.
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U2 - 10.1039/c8fd00164b
DO - 10.1039/c8fd00164b
M3 - Article
C2 - 30993272
AN - SCOPUS:85068532768
VL - 215
SP - 123
EP - 140
JO - Faraday Discussions
JF - Faraday Discussions
SN - 1364-5498
ER -