The vibrational and H-1 NMR data hints that the coordination of the
2,2'-dithiodipyridine (2-pySS) ligand to the Ru(CN)(5)(3-) metal
center occurs through the sulfur atom instead of the nitrogen atoms
which is usually observed for N-heterocyclic ligands. Electrochemical
results show that this coordination mode implies an additional
thermodynamic stabilization of the Ru-II over Ru-III oxidation state due
to a relative stronger pi-back-bonding interaction with the empty
low-lying d pi orbitals of the sulfur atom. Computational data reinforce
the experimental results showing that the 2-pySS Lewis base centers are
located on the sulfur atoms. Ligands containing only sulfur atoms as
coordination sites (2,2'-dithiodipyridine N-oxide (2-pySSNO),
1,4-dithiane (1,4-dt), and 2,6-dithiaspiro3.3heptane (asp)) were
also coordinated to the Ru(CN)(5)(3-) metal center to undoubtedly
correlate the electrochemical results with the ligand coordination atom.
Among the synthesized compounds, the Ru(CN)5(1,4-dt)3- and
Ru(CN)5(asp)3- complexes showed to be able to form self-assembled
monolayers (SAMs) on gold. These SAMs, which were characterized by SERS
(surface-enhanced Raman scattering) spectroscopy, successfully assessed
the heterogeneous electron transfer reaction of the cytochrome c
metalloprotein in physiological medium. (c) 2007 Elsevier B.V. All
rights reserved.
%0 Journal Article
%1 WOS:000248866700013
%A de Sousa, Jackson R
%A Diogenes, Izaura C N
%A Temperini, Marcia L A
%A Sales, Francisco A M
%A de Pinheiro, Solange O
%A Filho, Raimundo Costa N
%A de Andrade Junior, Jos S
%A de Moreira, Icaro S
%C PO BOX 564, 1001 LAUSANNE, SWITZERLAND
%D 2007
%I ELSEVIER SCIENCE SA
%J JOURNAL OF ORGANOMETALLIC CHEMISTRY
%K SAM; complexes; computational containing cyclic cytochrome c} ligands; ruthenium simulation; voltammetry; {sulfur
%N 17
%P 3691-3699
%R 10.1016/j.jorganchem.2007.05.024
%T Synthesis, characterization, and SAMs electroactivity of ruthenium
complexes with sulfur containing ligands
%V 692
%X The vibrational and H-1 NMR data hints that the coordination of the
2,2'-dithiodipyridine (2-pySS) ligand to the Ru(CN)(5)(3-) metal
center occurs through the sulfur atom instead of the nitrogen atoms
which is usually observed for N-heterocyclic ligands. Electrochemical
results show that this coordination mode implies an additional
thermodynamic stabilization of the Ru-II over Ru-III oxidation state due
to a relative stronger pi-back-bonding interaction with the empty
low-lying d pi orbitals of the sulfur atom. Computational data reinforce
the experimental results showing that the 2-pySS Lewis base centers are
located on the sulfur atoms. Ligands containing only sulfur atoms as
coordination sites (2,2'-dithiodipyridine N-oxide (2-pySSNO),
1,4-dithiane (1,4-dt), and 2,6-dithiaspiro3.3heptane (asp)) were
also coordinated to the Ru(CN)(5)(3-) metal center to undoubtedly
correlate the electrochemical results with the ligand coordination atom.
Among the synthesized compounds, the Ru(CN)5(1,4-dt)3- and
Ru(CN)5(asp)3- complexes showed to be able to form self-assembled
monolayers (SAMs) on gold. These SAMs, which were characterized by SERS
(surface-enhanced Raman scattering) spectroscopy, successfully assessed
the heterogeneous electron transfer reaction of the cytochrome c
metalloprotein in physiological medium. (c) 2007 Elsevier B.V. All
rights reserved.
@article{WOS:000248866700013,
abstract = {The vibrational and H-1 NMR data hints that the coordination of the
2,2'-dithiodipyridine (2-pySS) ligand to the [Ru(CN)(5)](3-) metal
center occurs through the sulfur atom instead of the nitrogen atoms
which is usually observed for N-heterocyclic ligands. Electrochemical
results show that this coordination mode implies an additional
thermodynamic stabilization of the Ru-II over Ru-III oxidation state due
to a relative stronger pi-back-bonding interaction with the empty
low-lying d pi orbitals of the sulfur atom. Computational data reinforce
the experimental results showing that the 2-pySS Lewis base centers are
located on the sulfur atoms. Ligands containing only sulfur atoms as
coordination sites (2,2'-dithiodipyridine N-oxide (2-pySSNO),
1,4-dithiane (1,4-dt), and 2,6-dithiaspiro[3.3]heptane (asp)) were
also coordinated to the [Ru(CN)(5)](3-) metal center to undoubtedly
correlate the electrochemical results with the ligand coordination atom.
Among the synthesized compounds, the [Ru(CN)5(1,4-dt)]3- and
[Ru(CN)5(asp)]3- complexes showed to be able to form self-assembled
monolayers (SAMs) on gold. These SAMs, which were characterized by SERS
(surface-enhanced Raman scattering) spectroscopy, successfully assessed
the heterogeneous electron transfer reaction of the cytochrome c
metalloprotein in physiological medium. (c) 2007 Elsevier B.V. All
rights reserved.},
added-at = {2022-05-23T20:00:14.000+0200},
address = {PO BOX 564, 1001 LAUSANNE, SWITZERLAND},
author = {de Sousa, Jackson R and Diogenes, Izaura C N and Temperini, Marcia L A and Sales, Francisco A M and de Pinheiro, Solange O and Filho, Raimundo Costa N and de Andrade Junior, Jos S and de Moreira, Icaro S},
biburl = {https://www.bibsonomy.org/bibtex/2d9196fc24bcec92859b1d68a0fd4ce47/ppgfis_ufc_br},
doi = {10.1016/j.jorganchem.2007.05.024},
interhash = {c6df36c183ea0d78b4e399976d1be0b5},
intrahash = {d9196fc24bcec92859b1d68a0fd4ce47},
issn = {0022-328X},
journal = {JOURNAL OF ORGANOMETALLIC CHEMISTRY},
keywords = {SAM; complexes; computational containing cyclic cytochrome c} ligands; ruthenium simulation; voltammetry; {sulfur},
number = 17,
pages = {3691-3699},
publisher = {ELSEVIER SCIENCE SA},
pubstate = {published},
timestamp = {2022-05-23T20:00:14.000+0200},
title = {Synthesis, characterization, and SAMs electroactivity of ruthenium
complexes with sulfur containing ligands},
tppubtype = {article},
volume = 692,
year = 2007
}