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

Abstract

The influence of a biologically inspired second and outer coordination sphere on Rh-bis(diphosphine) CO2 hydrogenation catalysts was explored.

Low-Dimensional Architectures in Isomeric cis-PtCl2{Ph2PCH2N(Ar)CH2PPh2} Complexes Using Regioselective-N(Aryl)-Group Manipulation

“…Unsurprisingly, the use of highly polar solvents (DMSO, CH 3 OH) in this study has been shown to play an important role in disrupting packing behaviour. Our work reinforces the importance of substituent effects, not only those commonly associated with −PR 2 groups which may be alkyl or aryl based [37,38], but also those functional moieties positioned on the arene group of the central tertiary amine.…”

Biohybrid Systems for Improved Bioinspired, Energy‐Relevant Catalysis

“…Each amino acid modification yielded a different turnover frequency (TOF), spanning a range that varied by a factor of four. [68] These rate differences were attributed to the outer coordination sphere resulting from amino acid substitution. From such studies, it is evident that even small biomolecule-derived ligands contribute to the local environment, promote the formation of higher-order structures, and influence the outer-sphere environment of the metal complexes.…”

“…In similar studies involving the incorporation of amino acid‐derived ligands, Shaw and co‐workers applied methyl ester‐modified amino acids (glycine, leucine, phenylalanine, aspartic acid, and histidine) to Rh‐bis(diphosphine) CO 2 hydrogenation catalysts. Each amino acid modification yielded a different turnover frequency (TOF), spanning a range that varied by a factor of four [68] . These rate differences were attributed to the outer coordination sphere resulting from amino acid substitution.…”

Light-Driven CO2 Reduction by Co-Cytochrome b562

“…Protein scaffolds may aide the efficiency of the organometallic center by offering tunable primary and secondary coordination spheres, by facilitating reactant binding and product release to and from the active site, and by protecting the organometallic center from degradation (Lu et al, 2009;Alcala-Torano et al, 2016;Schwizer et al, 2018;Davis and Ward, 2019;Nastri et al, 2019;Oohora et al, 2019;Vornholt et al, 2020). This approach has been used to produce water-soluble catalysts that are capable of producing hydrogen from protons under mild conditions, repurposing a diverse group of organometallic catalysts (Sano et al, 2011;Roy et al, 2012;Kleingardner et al, 2014;Onoda et al, 2014;Sommer et al, 2014;Sommer et al, 2016;Firpo et al, 2018;Call et al, 2019a;Slater et al, 2019;Walsh et al, 2019;Alvarez-Hernandez et al, 2020;Laureanti et al, 2020;Le et al, 2020;Roy et al, 2020). Comparatively little work has been carried out on the reduction of CO 2 by hybrid metalloenzymes: in one example nickel cyclam complexes anchored to azurin support catalytic CO 2 reduction, with evidence of protein modulation of activity compared to the isolated cyclam (Schneider and Shafaat, 2016;Liu et al, 2018;Schneider et al, 2018).…”