Ruthenium salen nitro and nitrosyl complexes: Synthesis, characterization and photochemical studies

INOR 209

Bridget T. Owens, bowens@chem.ucsb.edu1, Birgit Birkmann2, Susmita Bandyopadhyay1, Elia Tfouni3, and Peter C. Ford, ford@chem.ucsb.edu1. (1) Department of Chemistry and Biochemistry, University of California, Santa Barbara, Santa Barbara, CA 93106, (2) Institut für Anorganische und Analytische Chemie/Hahn Group, Universität Münster (WWU), Germany, Wilhelm Klemm Strasse 8, D-48149 Münster, Germany, (3) Departamento de Química, Faculdade de Filosofia Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Av. Bandeirantes, 3900, 14040-901, Ribeirão Preto, SP, Brazil

There is ongoing interest in the development of photochemical strategies for delivery of NO to biological targets.  Ruthenium nitrosyl complexes undergo NO dissociation when irradiated with UV light.  After NO release from [Ru(salen)(NO)(H2O)]+ the photoproduct, [RuIII(salen)(H2O)2]+ can be converted back to the parent complex in the presence of nitrite.  Our studies are concerned with understanding quantitatively the photochemical process as well as the interaction between ruthenium(III) and nitrite in the context of possible applications using endogenous nitrite to regenerate the NO precursor complex.  Reported is further characterization of [Ru(salen)(NO)(H2O)]+ including pKa, quantum yields, and electrochemical studies and the synthesis and characterization of a stable ruthenium(III) nitro species, [Ru(salen-x)(PPh3)(NO2)].  For example, the reaction of [Ru(salen)(PPh3)(Cl)] and AgNO2 with NBu4OH as a phase transfer agent gave a ruthenium nitro complex.  This reaction also resulted in nitration of the salen rings.  Salen nitration was not observed in the absence of Ag(I).  Possible mechanisms regarding this ring nitration are discussed.

 

 

General Inorganic Chemistry
7:00 PM-10:00 PM, Sunday, August 19, 2007 BCEC -- Exhibit Hall - B2, Poster

Division of Inorganic Chemistry

The 234th ACS National Meeting, Boston, MA, August 19-23, 2007