title: Bio-inspired CO2reduction by a rhenium tricarbonyl bipyridine-based catalyst appended to amino acids and peptidic platforms: incorporating proton relays and hydrogen-bonding functional groups.
abstract: Herein, we report a new approach to bio-inspired catalyst design. The molecular catalyst employed in these studies is based on the robust and selective Re(bpy)(CO)3Cl-type (bpy = 2,2'-bipyridine) homogeneous catalysts, which have been extensively studied for their ability to reduce CO2electrochemically or photochemically in the presence of a photosensitizer. These catalysts can be highly active photocatalysts in their own right. In this work, the bipyridine ligand was modified with amino acids and synthetic peptides. These results build on earlier findings wherein the bipyridine ligand was functionalized with amide groups to promote dimer formation and CO2reduction by an alternate bimolecular mechanism at lower overpotential (ca. 250 mV) than the more commonly observed unimolecular process. The bio-inspired catalysts were designed to allow for the incorporation of proton relays to support reduction of CO2to CO and H2O. The coupling of amino acids tyrosine and phenylalanine led to the formation of two structurally similar Re catalyst/peptide catalysts for comparison of proton transport during catalysis. This article reports the synthesis and characterization of novel catalyst/peptide hybrids by molecular dynamics (MD simulations of structural dynamics), NMR studies of solution phase structures, and electrochemical studies to measure the activities of new bio-inspired catalysts in the reduction of CO2.
authors.affiliation: University of California, Department of Chemistry and Biochemistry, 9500 Gilman Drive, La Jolla, San Diego, California 92093, USA. ckubiak@ucsd.edu.
authors.forename: S A
authors.initials: SA
authors.lastname: Chabolla
authors.forename: C W
authors.initials: CW
authors.lastname: Machan
authors.forename: J
authors.initials: J
authors.lastname: Yin
authors.forename: E A
authors.initials: EA
authors.lastname: Dellamary
authors.forename: S
authors.initials: S
authors.lastname: Sahu
authors.forename: N C
authors.initials: NC
authors.lastname: Gianneschi
authors.forename: M K
authors.initials: MK
authors.lastname: Gilson
authors.forename: F A
authors.initials: FA
authors.lastname: Tezcan
authors.forename: C P
authors.initials: CP
authors.lastname: Kubiak
mesh_terms: D000596:Amino Acids / Q000138:chemical synthesis* / Q000737:chemistry; D002245:Carbon Dioxide / Q000737:chemistry* / Q000378:metabolism; D002384:Catalysis; D006860:Hydrogen Bonding; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010455:Peptides / Q000138:chemical synthesis* / Q000737:chemistry; D011522:Protons
chemical_list: D000596:Amino Acids; D009942:Organometallic Compounds; D010455:Peptides; D011522:Protons; C550637:tricarbonyl(2,2'-bipyridine)rhenium(I); D002245:Carbon Dioxide