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Electrochemical Investigation of the Kinetics of Chloride Substitution upon Reduction of [Ru(porphyrin)(NO)Cl] Complexes in Tetrahydrofuran
Author(s) -
Zink Jeremy R.,
Abucayon Erwin G.,
Ramuglia Anthony R.,
Fadamin Arghavan,
Eilers James E.,
RichterAddo George B.,
Shaw Michael J.
Publication year - 2018
Publication title -
chemelectrochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.182
H-Index - 59
ISSN - 2196-0216
DOI - 10.1002/celc.201701001
Subject(s) - tetrahydrofuran , chemistry , porphyrin , chloride , ruthenium , electrochemistry , reaction rate constant , equilibrium constant , photochemistry , inorganic chemistry , electron paramagnetic resonance , kinetics , lithium chloride , organic chemistry , catalysis , electrode , nuclear magnetic resonance , solvent , physics , quantum mechanics
The electrochemistry of several ruthenium porphyrin nitrosyl chloride complexes [Ru(por)(NO)Cl] have been examined in tetrahydrofuran (THF). The complexes undergo one‐electron irreversible reductions, which result in diffusion‐limited substitutions of the chloride ligands for THF. This chloride metathesis is reversible in the presence of added NBu 4 Cl, 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 favoring 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 approximately 10 18 enhancement of the rates of chloride loss.