Uncoupled Redox-Inactive Lewis Acids in the Secondary
Coordination Sphere Entice Ligand-Based Nitrite Reduction
Version 2 2018-04-04, 14:51
Version 1 2018-04-02, 18:03
Posted on 2018-04-04 - 14:51
Metal complexes composed
of redox-active pyridinediimine (PDI) ligands are capable of forming
ligand-centered radicals. In this Forum article, we demonstrate that
integration of these types of redox-active sites with bioinspired
secondary coordination sphere motifs produce direduced complexes,
where the reduction potential of the ligand-based redox sites is uncoupled
from the secondary coordination sphere. The utility of such ligand
design was explored by encapsulating redox-inactive Lewis acidic cations
via installation of a pendant benzo-15-crown-5 in the secondary coordination
sphere of a series of Fe(PDI) complexes. Fe(15bz5PDI)(CO)2 was shown to encapsulate the redox-inactive alkali ion, Na+, causing only modest (31 mV) anodic shifts in the ligand-based
redox-active sites. By uncoupling the Lewis acidic sites from the
ligand-based redox sites, the pendant redox-inactive ion, Na+, can entice the corresponding counterion, NO2–, for reduction to NO. The subsequent initial rate analysis reveals
an acceleration in anion reduction, confirming this hypothesis.
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
Burns, Kyle T.; Marks, Walker R.; Cheung, Pui Man; Seda, Takele; Zakharov, Lev N.; Gilbertson, John D. (2018). Uncoupled Redox-Inactive Lewis Acids in the Secondary
Coordination Sphere Entice Ligand-Based Nitrite Reduction. ACS Publications. Collection. https://doi.org/10.1021/acs.inorgchem.8b00032
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 (6)
KB
Kyle T. Burns
WM
Walker R. Marks
PC
Pui Man Cheung
TS
Takele Seda
LZ
Lev N. Zakharov
JG
John D. Gilbertson
KEYWORDS
Naligand-based redox sitespendant redox-inactive ionligand-based redox-active sitespendant benzo -15-crownFeUncoupled Redox-Inactive Lewis AcidsPDIcoordination sphere motifsencapsulating redox-inactive Lewis acidic cationsLewis acidic sitesredox-inactive alkali ioncoordination sphereSecondary Coordination Sphere Entice Ligand-Based Nitrite Reduction Metal complexes