Variation of electrode potential and charge transfer bands in series of tetravalent ruthenium complexes [RuCl6-n(PrCN)n]n-2

Junie B. Billones; Eva Marie A. Ratilla; Graham A. Heath

doi:10.1016/j.ica.2015.02.011

Variation of electrode potential and charge transfer bands in series of tetravalent ruthenium complexes [RuCl₆_-n(PrCN)_n]ⁿ^-²

Junie B. Billones^*, Eva Marie A. Ratilla, Graham A. Heath

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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Abstract

A truncated series of ruthenium(IV) complexes [RuCl₍₆_-_n₎(RCN)_n]ⁿ^-² (n = 0-3; R = n-propyl) has been electrogenerated in situ and characterized spectroscopically. This substitution series allowed the examination of the variation of electrode potential of Ru⁺⁴/Ru⁺³ couple and the accompanying trends in ligand-to-metal charge-transfer (LMCT) spectra. The Cl → Ru⁴⁺ charge transfer manifold red-shifted from n = 0-2, and then moved back to the blue edge upon the third substitution of chloride with nitrile. Moreover, the anodic shift in Ru⁺⁴/Ru⁺³ redox couple upon the third chloride replacement was barely half the expected change. These irregular trends contradict the results of the DFT studies and the tenet of ligand additivity principle.

Original language	English
Pages (from-to)	209-215
Number of pages	7
Journal	Inorganica Chimica Acta
Volume	429
DOIs	https://doi.org/10.1016/j.ica.2015.02.011
Publication status	Published - 1 Apr 2015

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title = "Variation of electrode potential and charge transfer bands in series of tetravalent ruthenium complexes [RuCl6-n(PrCN)n]n-2",

abstract = "A truncated series of ruthenium(IV) complexes [RuCl(6-n)(RCN)n]n-2 (n = 0-3; R = n-propyl) has been electrogenerated in situ and characterized spectroscopically. This substitution series allowed the examination of the variation of electrode potential of Ru+4/Ru+3 couple and the accompanying trends in ligand-to-metal charge-transfer (LMCT) spectra. The Cl → Ru4+ charge transfer manifold red-shifted from n = 0-2, and then moved back to the blue edge upon the third substitution of chloride with nitrile. Moreover, the anodic shift in Ru+4/Ru+3 redox couple upon the third chloride replacement was barely half the expected change. These irregular trends contradict the results of the DFT studies and the tenet of ligand additivity principle.",

keywords = "Charge transfer spectra, DFT study, Electrode potentials, Ligand effects, Ruthenium(IV) complexes",

author = "Billones, \{Junie B.\} and Ratilla, \{Eva Marie A.\} and Heath, \{Graham A.\}",

note = "Publisher Copyright: {\textcopyright} 2015 Published by Elsevier B.V.",

year = "2015",

month = apr,

day = "1",

doi = "10.1016/j.ica.2015.02.011",

language = "English",

volume = "429",

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T1 - Variation of electrode potential and charge transfer bands in series of tetravalent ruthenium complexes [RuCl6-n(PrCN)n]n-2

AU - Billones, Junie B.

AU - Ratilla, Eva Marie A.

AU - Heath, Graham A.

PY - 2015/4/1

Y1 - 2015/4/1

N2 - A truncated series of ruthenium(IV) complexes [RuCl(6-n)(RCN)n]n-2 (n = 0-3; R = n-propyl) has been electrogenerated in situ and characterized spectroscopically. This substitution series allowed the examination of the variation of electrode potential of Ru+4/Ru+3 couple and the accompanying trends in ligand-to-metal charge-transfer (LMCT) spectra. The Cl → Ru4+ charge transfer manifold red-shifted from n = 0-2, and then moved back to the blue edge upon the third substitution of chloride with nitrile. Moreover, the anodic shift in Ru+4/Ru+3 redox couple upon the third chloride replacement was barely half the expected change. These irregular trends contradict the results of the DFT studies and the tenet of ligand additivity principle.

AB - A truncated series of ruthenium(IV) complexes [RuCl(6-n)(RCN)n]n-2 (n = 0-3; R = n-propyl) has been electrogenerated in situ and characterized spectroscopically. This substitution series allowed the examination of the variation of electrode potential of Ru+4/Ru+3 couple and the accompanying trends in ligand-to-metal charge-transfer (LMCT) spectra. The Cl → Ru4+ charge transfer manifold red-shifted from n = 0-2, and then moved back to the blue edge upon the third substitution of chloride with nitrile. Moreover, the anodic shift in Ru+4/Ru+3 redox couple upon the third chloride replacement was barely half the expected change. These irregular trends contradict the results of the DFT studies and the tenet of ligand additivity principle.

KW - Charge transfer spectra

KW - DFT study

KW - Electrode potentials

KW - Ligand effects

KW - Ruthenium(IV) complexes

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U2 - 10.1016/j.ica.2015.02.011

DO - 10.1016/j.ica.2015.02.011

M3 - Article

SN - 0020-1693

VL - 429

SP - 209

EP - 215

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

ER -

Variation of electrode potential and charge transfer bands in series of tetravalent ruthenium complexes [RuCl₆_-n(PrCN)_n]ⁿ^-²

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