1 Synthesis, Electrochemical and Synthesis, Electrochemical and Spectroscopic Characterization of Spectroscopic Characterization of Diruthenium Complexes with Diruthenium Complexes with Mixed Anionic Bridging Ligands Mixed Anionic Bridging Ligands Rachel Garcia SACNAS National Conference Friday, October 27, 2006 Department of Chemistry University of Houston
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Synthesis, Electrochemical and Synthesis, Electrochemical and Spectroscopic Characterization of Spectroscopic Characterization of
Diruthenium Complexes with Diruthenium Complexes with Mixed Anionic Bridging LigandsMixed Anionic Bridging Ligands
Rachel Garcia
SACNAS National Conference
Friday, October 27, 2006
Department of Chemistry
University of Houston
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RuRu22 complex components complex components
RuRu22(O(O22CCHCCH33))44ClCl
Anionic bridging ligands Anionic bridging ligands surround the Rusurround the Ru22
5+5+ core which core which
also can be replaced by other also can be replaced by other bridging ligandsbridging ligands
Ru2 core in a 5+ oxidation state; are redox active
Contains an axial ligand which can be replaced by other ligands
ORTEP from Bear et al. Inorg. Chem. 2001, 40, 2282-2286
2-fluoroanilino pyridinate
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ObjectiveObjective
How do the electrochemical and spectroelectrochemical properties How do the electrochemical and spectroelectrochemical properties change as you increasingly replace one acetate by Fap?change as you increasingly replace one acetate by Fap?
IntermediatesIntermediates
a) Ru2(O2CCH3)3(Fap)Cl b) Ru2(O2CCH3)2(Fap)2Cl c)Ru2(O2CCH3)(Fap)3Cl
The mixed ligand series, Ru2(ac)x(Fap)y where x+y = 4, were synthesized
Electrochemical studies reveal a negative shift for the 1st reduction and 1st oxidation, which can be explained by the increase of electron density around the diruthenium core as you replace the ac by Fap.
Linear relationships have been established between the number Fap ligands (the Hammet constant of fluorine) bound to the diruthenium core and the redox processes, Ru2
5+/4+ and Ru25+/6+.
With only 2 Fap’s bound to the core, spectral changes of the reduced and oxidized forms of a complex are similar to a complex with 4 Fap/s around the dimetal core.
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AcknowledgementsAcknowledgements
Dr. Kadish, my thesis advisor- for all of his help Dr. Kadish, my thesis advisor- for all of his help and support academically and financiallyand support academically and financially
Dr. “V” (Van Caemelbecke) from Houston Baptist Dr. “V” (Van Caemelbecke) from Houston Baptist University- for his great academic advice and helpUniversity- for his great academic advice and help
Dr. Chan, UH director of AGEP- financial plus Dr. Chan, UH director of AGEP- financial plus personal support and an opportunity to be here at personal support and an opportunity to be here at SACNAS SACNAS