Рад у часопису

објављена верзија

енглески

Aleksandar Mijatović, Biljana Šmit, Ana Rilak, Biljana Petrović, Dragan Čanović, Živadin D. Bugarčić

NMR kinetic studies of the interactions between [Ru(terpy)(bipy)(H2O)]2+ and some sulfur-donor ligands

Inorganica Chimica Acta

Elsevier BV

2012

Reakcije supstitucije monofunkcionalnog [Ru(terpi)(bipi)(H2O)]2+ kompleksa, gde je terpi = 2,2′:6′,2″-terpiridin i bipi = 2,2′-bipiridin, sa biološki relevantnim sumporo donorskim ligandima, kao što su tiourea, l-metionin, l-cistein i glutation, proučavane su u vodenim rastvorima tehnikom 1H i 13C NMR spektroskopije. Sve reakcije su proučavajne na pH 7,4, u prisustvu fosfatnog pufera, da bi se oponašalo fiziološko okruženje tokom procesa supstitucije. Reakcije se izvode na 295 K pod uslovima reakcija drugog reda. Uočeni rezultati pokazuju da brzina supstitucije snažno zavisi od tipa i strukture ulaznog nukleofila. Dobijeni red reaktivnosti za ulazne sumpor donorske ligande je: tiourea > l-metionin > l-cistein > glutation. Vrednost pKa koordinisanog vodenog liganda određena je u D2O 1H NMR tehnikom. Ovi rezultati potvrđuju snažan uticaj inertnih polipiridilnih liganada na hemijsko ponašanje Ru(II) kompleksa, kao i njihov uticaj na labilnost koordinisanog molekula vode.

Substitution reactions of monofunctional [Ru(terpy)(bipy)(H2O)]2+ complex, where terpy = 2,2′:6′,2″-terpyridine and bipy = 2,2′-bipyridine, with biologically relevant sulfur-donor nucleophiles, such as thiourea, l-methionine, l-cysteine and glutathione, are studied in aqueous solutions by 1H and 13C NMR spectroscopy techniques. All reactions are studied at pH 7.4, in the presence of phosphate buffer, to mimic the physiological environment during the substitution process. The reactions are carried out at 295 K under the second-order conditions. Observed results show that the rate of substitution strongly depends on the type and the structure of the entering nucleophile. The obtained order of reactivity for the entering sulfur-donor ligands is: thiourea > l-methionine > l-cysteine > glutathione. The pKa value of coordinated water ligand was determined in D2O by the 1H NMR technique. These results confirm the strong influence of inert polypyridyl ligands on the chemical behavior of Ru(II) complex as well as their influence on the lability of coordinated water molecule.

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10.1016/j.ica.2012.09.016

0020-1693

Materials Chemistry,Inorganic Chemistry,Physical and Theoretical Chemistry

Materials Chemistry,Inorganic Chemistry,Physical and Theoretical Chemistry

https://api.elsevier.com/content/article/PII:S0020169312005506?httpAccept=text/xml

M20

М22

Отворени приступ

Creative Commons – Attribution-NonComercial-No Derivative Works 4.0 International

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