Developing catalysts for the electrochemical reduction of carbon dioxide is of great interest in the field of inorganic chemistry because of the potential for the creation of carbon feedstocks from renewable sources. Catalysts of the type [Re(bpy)(CO)3X]n (n = +1, 0; X = CO, CH3CN, Cl–, OTf–; bpy = 2,2'-bipyridyl and analogues thereof) have been studied in recent decades for their capacity to catalytically reduce CO2, a greenhouse gas, into potentially useful industrial feedstocks such as CO, which may be converted to higher value fuels in the Fischer-Tropsch process. These complexes are competent electrocatalysts and photocatalysts for the reduction of carbon dioxide by two electrons. In addition to renewable energy, mimicking mechanisms (such as hydrogen bonding and pendant base positioning) used by nature to drive the selectivity and efficiency of enzymes has been of great interest to the field of molecular catalysis. We have incorporated Re(bpy)(CO)3Cl onto peptidic platforms in attempts to understand and optimize the effects these interactions have on the CO2 reduction reaction. By asymmetrically modifying the bipyridine ligand and attaching it to the side-chain of an N-terminal Fmoc-protected glutamic acid it is possible to generate a non-natural amino acid catalyst that can be used in solid phase peptide synthesis. These robust catalysts retain their functionality for the reduction of CO2 after common peptide synthesis techniques and exhibit catalytic properties that may be tuned by the composition of the peptide structure. Infrared spectroelectrochemical measurements indicate that these emergent properties can be the result of peptide-peptide or peptide-substrate interactions and are dependent on the choice of solvent. To our knowledge, this is the first organometallic electrocatalyst that can be incorporated into solid phase peptide synthesis.

Design and investigations of peptidic platforms on the electrocatalytic reduction of carbon dioxide by a rhenium bipyridine-based complex

251st National Meeting (2016)

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