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DOE OSTI · 1052924

Active Hydrogenation Catalyst with a Structured, Peptide-Based Outer-Coordination Sphere

Jain, Avijita·Buchko, Garry W·Reback, Matthew L·O'Hagan, Molly J·Ginovska-Pangovska, Bojana·Linehan, John C·Shaw, Wendy J
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Abstract

The synthesis, catalytic activity, and structural features of a rhodium-based hydrogenation catalyst containing a phosphine ligand coupled to a 14-residue peptide are reported. Both CD and NMR spectroscopy show that the peptide adopts a helical structure in 1:1:1 TFE/MeCN/H2O that is maintained when the peptide is attached to the ligand and when the ligand is attached to the metal complex. The metal complex hydrogenates aqueous solutions of 3-butenol to 1-butanol at 360 ± 50 turnovers/Rh/h at 294 K. This peptide- based catalyst represents a starting point for developing and characterizing a peptide-based outer-coordination sphere that can be used to introduce enzyme-like features into molecular catalysts. This work was funded by the US DOE Basic Energy Sciences, Chemical Sciences, Geoscience and Biosciences Division (AJ, JCL and WJS), the Office of Science Early Career Research Program through the Office of Basic Energy Sciences (GWB, MLR and WJS). Part of the research was conducted at the W.R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by U.S. Department of Energy’s Office of Biolog-ical and Environmental Research (BER) program located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the U.S. Department of Energy.

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amino acid catalystsartificial enzymebioinspiredcatalysisEnvironmental Molecular Sciences Laboratoryhydrogenation catalysis

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Jain, Avijita, Buchko, Garry W, Reback, Matthew L, O'Hagan, Molly J, Ginovska-Pangovska, Bojana, Linehan, John C, Shaw, Wendy J. 2012-10-05. Active Hydrogenation Catalyst with a Structured, Peptide-Based Outer-Coordination Sphere. https://doi.org/10.1021/cs3004177

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DOE OSTI2014

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DOE OSTI2013

The Role of a Dipeptide Outer-Coordination Sphere on H2 -Production Catalysts: Influence on Catalytic Rates and Electron Transfer

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DOE OSTI2012

Incorporating Amino Acid Esters into Catalysts for Hydrogen Oxidation: Steric and Electronic Effects and the Role of Water as a Base

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