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Evaluating the impacts of amino acids in the second and outer coordination spheres of Rh bis(diphosphine) complexes for CO2 hydrogenation

Abstract

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 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), phenylalanine methyl ester (PheOMe)), one acidic (aspartic acid dimethyl ester (AspOMe)) and one basic (histidine methyl ester (MeHisOMe)) amino acid esters. The turn over frequencies (TOFs) for CO2 hydrogenation for each of these complexes was compared to 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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Publication details

The article was accepted on 23 Nov 2018 and first published on 30 Nov 2018


Article type: Paper
DOI: 10.1039/C8FD00164B
Citation: Faraday Discuss., 2018, Accepted Manuscript
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    Evaluating the impacts of amino acids in the second and outer coordination spheres of Rh bis(diphosphine) complexes for CO2 hydrogenation

    A. P. Walsh, J. A. Laureanti, S. Katipamula, G. M. Chambers, N. Priyadarshani, S. Lense, T. Bays, J. C. Linehan and W. Shaw, Faraday Discuss., 2018, Accepted Manuscript , DOI: 10.1039/C8FD00164B

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