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Acidity and photolability of ruthenium salen nitrosyl and aquo complexes in aqueous solutions |
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| Authors: | J. Bordini I.E. Borissevitch P.C. Ford |
| Affiliation: | a Departamento de Química, Faculdade de Filosofia Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Av. Bandeirantes 3900, CEP 14040-901, Ribeirão Preto, SP, Brazil b Departamento de Física e Matemática, Faculdade de Filosofia Ciência e Letras de Ribeirão Preto, Universidade de São Paulo, Av. Bandeirantes 3900, CEP 14040-901, Ribeirão Preto, SP, Brazil c Department of Chemistry and Biochemistry, University of California, Santa Barbara, CA 93106-9510, USA |
| Abstract: | The photochemical behavior of nitrosyl complexes Ru(salen)(NO)(OH2)+ and Ru(salen)(NO)Cl (salen = N,N′-ethylenebis-(salicylideneiminato) dianion) in aqueous solution is described. Irradiation with light in the 350-450 nm range resulted in nitric oxide (NO) release from both. For Ru(salen)(NO)Cl secondary photoreactions also resulted in chloride aquation. Thus, in both cases the final photoproduct is the diaquo cation  , for which pKa’s of 5.9 and 9.1 were determined for the coordinated waters. The pKa of the Ru(salen)(NO)(OH2)+ cation was also determined as 4.5 ± 0.1, and the relative acidities of these ruthenium aquo units are discussed in the context of the bonding interactions between Ru(III) and NO. |
| Keywords: | Chloride Photolability Photorelease Ruthenium Salen Schiff base Nitrosyl Complexes Photochemistry Nitric oxide Donor Nitrosonium Acidity Coordinated water Sequential photoreactions |
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