Unknown

Dataset Information

0

Uncoupled Redox-Inactive Lewis Acids in the Secondary Coordination Sphere Entice Ligand-Based Nitrite Reduction.


ABSTRACT: 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.

SUBMITTER: Burns KT 

PROVIDER: S-EPMC6102076 | biostudies-literature | 2018 Aug

REPOSITORIES: biostudies-literature

altmetric image

Publications

Uncoupled Redox-Inactive Lewis Acids in the Secondary Coordination Sphere Entice Ligand-Based Nitrite Reduction.

Burns Kyle T KT   Marks Walker R WR   Cheung Pui Man PM   Seda Takele T   Zakharov Lev N LN   Gilbertson John D JD  

Inorganic chemistry 20180402 16


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 acidi  ...[more]

Similar Datasets

| S-EPMC7606458 | biostudies-literature
| S-EPMC10023486 | biostudies-literature
| S-EPMC9633411 | biostudies-literature
| S-EPMC10055695 | biostudies-literature
| S-EPMC8156824 | biostudies-literature
| S-EPMC5304617 | biostudies-literature
| S-EPMC3654670 | biostudies-literature
| S-EPMC5490426 | biostudies-literature
| S-EPMC7221517 | biostudies-literature
| S-EPMC2772092 | biostudies-literature