Double Hangman Iron Porphyrin and the Effect of Electrostatic
Nonbonding Interactions on Carbon Dioxide Reduction
Posted on 2020-02-24 - 13:51
Hangman
porphyrins influence the reaction rates of small molecule
activation by positioning a functional group in the secondary coordination
sphere of the metal center. Electrocatalysis by hangman porphyrins
has examined only one face modification of the macrocycle with a hanging
group, thus allowing for circumvention of secondary sphere effects
by reaction of the small molecule on the opposite face of the hangman
cleft. We now report the synthesis and characterization of a double
hangman Fe porphyrin in which both faces of the macrocycle are modified
with a hanging group. With this double hangman architecture, we are
able to unequivocally examine the role of electrostatic interactions
on the carbon dioxide reduction reaction (CO2RR) and show
that CO2RR rates are significantly attenuated, consistent
with the initial reduction of CO2 to generate the anion,
whose binding is diminished within the negatively charged carboxylic
groups of the hangman cleft. The results demonstrate the pronounced
role that nonbonding electrostatic interactions may play in CO2RR and highlight the need to manage deleterious electrostatic
interactions during catalytic turnover.
CITE THIS COLLECTION
DataCite
3 Biotech
3D Printing in Medicine
3D Research
3D-Printed Materials and Systems
4OR
AAPG Bulletin
AAPS Open
AAPS PharmSciTech
Abhandlungen aus dem Mathematischen Seminar der Universität Hamburg
ABI Technik (German)
Academic Medicine
Academic Pediatrics
Academic Psychiatry
Academic Questions
Academy of Management Discoveries
Academy of Management Journal
Academy of Management Learning and Education
Academy of Management Perspectives
Academy of Management Proceedings
Academy of Management Review
Margarit, Charles
G.; Asimow, Naomi G.; Gonzalez, Miguel I.; Nocera, Daniel G. (2020). Double Hangman Iron Porphyrin and the Effect of Electrostatic
Nonbonding Interactions on Carbon Dioxide Reduction. ACS Publications. Collection. https://doi.org/10.1021/acs.jpclett.9b03897
or
Select your citation style and then place your mouse over the citation text to select it.
SHARE
Usage metrics
Read the peer-reviewed publication
AUTHORS (4)
CM
Charles
G. Margarit
NA
Naomi G. Asimow
MG
Miguel I. Gonzalez
DN
Daniel G. Nocera