Hemilabile Proton Relays and Redox Activity Lead to {FeNO} x and Significant Rate Enhancements in NO2- Reduction.
J Am Chem Soc
; 140(49): 17040-17050, 2018 12 12.
Article
em En
| MEDLINE
| ID: mdl-30427681
ABSTRACT
Incorporation of the triad of redox activity, hemilability, and proton responsivity into a single ligand scaffold is reported. Due to this triad, the complexes Fe(PyrrPDI)(CO)2 (3) and Fe(MorPDI)(CO)2 (4) display 40-fold enhancements in the initial rate of NO2- reduction, with respect to Fe(MeOPDI)(CO)2 (7). Utilizing the proper sterics and p Ka of the pendant base(s) to introduce hemilability into our ligand scaffolds, we report unusual {FeNO} x mononitrosyl iron complexes (MNICs) as intermediates in the NO2- reduction reaction. The {FeNO} x species behave spectroscopically and computationally similar to {FeNO}7, an unusual intermediate-spin Fe(III) coupled to triplet NO- and a singly reduced PDI ligand. These {FeNO} x MNICs facilitate enhancements in the initial rate.
Texto completo:
1
Base de dados:
MEDLINE
Assunto principal:
Prótons
/
Complexos de Coordenação
/
Nitritos
Idioma:
En
Ano de publicação:
2018
Tipo de documento:
Article