Isotope effect profiles in the N-demethylation of N,N-dimethylanilines: a key to determine the pK(a) of nonheme Fe(III)-OH complexes

Alessia Barbieri; Martina De Gennaro; Stefano Di Stefano; Osvaldo Lanzalunga; Andrea Lapi; Marco Mazzonna; Giorgio Olivo; Barbara Ticconi

doi:10.1039/c5cc00411j

Isotope effect profiles in the N-demethylation of N,N-dimethylanilines: a key to determine the pK(a) of nonheme Fe(III)-OH complexes

Chem Commun (Camb). 2015 Mar 25;51(24):5032-5. doi: 10.1039/c5cc00411j.

Authors

Alessia Barbieri¹, Martina De Gennaro, Stefano Di Stefano, Osvaldo Lanzalunga, Andrea Lapi, Marco Mazzonna, Giorgio Olivo, Barbara Ticconi

Affiliation

¹ Dipartimento di Chimica, Sapienza Università di Roma and Istituto CNR di Metodologie Chimiche (IMC-CNR), Sezione Meccanismi di Reazione, c/o Dipartimento di Chimica, Sapienza Università di Roma, P.le A. Moro 5, I-00185 Rome, Italy. [email protected].

PMID: 25706886
DOI: 10.1039/c5cc00411j

Abstract

N-demethylation of N,N-dimethylanilines promoted by [(N4Py)Fe(IV)=O](2+) occurs by an electron transfer-proton transfer (ET-PT) mechanism with a rate determining PT step. From the bell-shaped curve of the KDIE profile it has been estimated that the pK(a) of [(N4Py)Fe(III)-OH](2+) is 9.7.

MeSH terms

Aniline Compounds / chemistry*
Deuterium / chemistry*
Electron Transport
Ferric Compounds / chemistry*
Hydrogen-Ion Concentration
Hydroxides / chemistry*
Methylation
Molecular Structure
Protons

Substances

Aniline Compounds
Ferric Compounds
Hydroxides
Protons
N,N-dimethylaniline
hydroxide ion
Deuterium