Aspetti meccanicistici della coordinazione di [(PPh3)3Ru(CO)(H2)] com Timina Acido Acetico

Di Iulio, Stefano (2016) Aspetti meccanicistici della coordinazione di [(PPh3)3Ru(CO)(H2)] com Timina Acido Acetico. [Laurea magistrale], Università di Bologna, Corso di Studio in Chimica industriale [LM-DM270]
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Ruthenium complexes have proved to exhibit antineoplastic activity related to the interaction of metal ion with DNA nucleobases. It is indeed of great interest to provide new insights on theses cutting-edge studies, such as the identification of distinct coordinative modes of DNA binding sites. During the investigation on the reaction between [(PPh3)3Ru(CO)(H)2], 1, and the Thymine Acetic Acid (THA) as model for nucleobases, we identified an unstable monohapto hydride acetate complex 2, which rapidly evolves into elusive intermediates whose nature was evidenced by NMR spectra and DFT calculations. We obtained crystals of [(PPh3)2Ru(CO)(k1-THA)(k2-THA)] 17, and [Ru(CO)(PPh3)2(k2-N,O)-[THA(A)];(k1-O)[THA(B)]2 18, phosphine ligands assuming cis conformation. The thesis deals on the analogue reactions of 1 with acetic acid by varying different parameters and operating conditions. The reaction yields to the hydride dihapto-acetate [(PPh3)2RuH(CO)(k2-Ac)] 8 through the related meridian monohapto, by releasing of phosphine ligand. However, the reaction yields a mixture of compounds, in which the dihapto hydride complex 8 is prevailing in any cases and does not provide any disclosure for the proposed mechanistic aspects. The reaction with two equivalents of acetic acid, affords the complex [(PPh3)2Ru(CO)(k1-Ac)(k2-Ac)] 11, exhibiting mutual trans:cis locations in 2:1 ratio for the phosphine. Such evidence agrees with the results obtained DFT calculations in vacuo, whereas it is in contrast with those obtained with the THA. Therefore we can inferred that the products obtained from the latter reaction is intermolecularly ruled by the hydrogen binding interactions between the functions [-NH•••(O)C-] in the two coordinated thymine ligands.

Tipologia del documento
Tesi di laurea (Laurea magistrale)
Autore della tesi
Di Iulio, Stefano
Relatore della tesi
Correlatore della tesi
Corso di studio
Ordinamento Cds
Parole chiave
ruthenium complexes thymine coordination mechanistic studies acetic acid
Data di discussione della Tesi
11 Ottobre 2016

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