%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 }