Electrochemical investigation of the kinetics of chloride substitution upon reduction of [Ru(porphyrin)(NO)Cl] complexes in THF.

Authors

Jeremy R. Zink, University of Oklahoma Norman CampusFollow
E G. Abucayon, University of Oklahoma
Anthony R. Ramuglia, Southern Illinois University EdwardsvilleFollow
Arghavan Fadamin, SIUE
James E. Eilers, Southern Illinois University EdwardsvilleFollow
George B. Richter-Addo, University of Oklahoma Norman Campus
Michael J. Shaw, Southern Illinois University at EdwardsvilleFollow

Document Type

Article

Publication Date

2018

Publication Title

ChemElectroChem

Department

Chemistry

Abstract

The electrochemistry of several ruthenium porphyrin nitrosyl chloride complexes [Ru(por)(NO)Cl] have been examined in tetrahydrofuran. The complexes undergo 1-electron irreversible reductions which result in the diffusion-limited substitutions of the chloride ligands for THF. This chloride metathesis is reversible in the presence of added NBu₄Cl, and equilibrium constants and rate constants for chloride loss have been estimated. These parameters correlate with the NO stretching frequencies of the parent complexes, with more electron-donating porphyrin ligands favouring chloride loss from the reduced complexes. The [Ru(por)(NO)(THF)] products of the reductions can be detected by IR, EPR and visible spectroscopies. These species undergo three further reductions, with good reversibility at scan rates >0.40 V s^-1. The [Ru(por)(NO)(THF)]^+/0 couples have also been determined, and the rate constants and equilibrium constants for recombination with chloride have been estimated. One-electron reductions of the [Ru(por)(NO)Cl] complexes result in ~10¹⁸ enhancement of the rates of chloride loss.

Recommended Citation

Zink, Jeremy R.; Abucayon, E G.; Ramuglia, Anthony R.; Fadamin, Arghavan; Eilers, James E.; Richter-Addo, George B.; and Shaw, Michael J., "Electrochemical investigation of the kinetics of chloride substitution upon reduction of [Ru(porphyrin)(NO)Cl] complexes in THF." (2018). SIUE Faculty Research, Scholarship, and Creative Activity. 74.
https://spark.siue.edu/siue_fac/74