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- Ericson, Anna, et al.
(author)
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Kinetics for interaction of the thione unit in 4-thio-2'-deoxyuridine and 4-thiouridine 5'-monophosphate with rapidly reacting gold(III) complexes
- 1998
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In: Journal of the Chemical Society. Dalton Transactions. - 1472-7773. ; 1998, s. 1687-1692
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Journal article (peer-reviewed)abstract
- Reactions of 4-thio-2′-deoxyuridine d(s4U) and 4-thiouridine 5′-monophosphate s4UMP with trans-[AuY2Cl2]+/– (Y = CN– or NH3) have been investigated by conventional and high-pressure stopped-flow spectrophotometry in aqueous solution with 2.9 ⩽ pH ⩽ 7.0. For a given combination of metal complex and sulfur donor the observed second-order rate constants decreased with increasing pH. In the pH range 2.9 to 5.5 this decrease is mainly due to displacement of the pH-dependent equilibrium trans-[AuY2Cl2]+/– + H2O ⇌ trans-[AuY2Cl(OH)]+/– + Cl– + H+ and formation of an increasing fraction of the less reactive gold(III) hydroxo complex. The activation parameters ΔH ‡, ΔS ‡ and ΔV ‡ at pH 4.0 for substitution of chloride for thione at trans-[AuY2Cl2]+/– indicate an associative interchange process. When the thione-containing nucleotide reacts with the cation, steric and electrostatic interactions between the metal complex and the phosphate group oppose each other and the rate of the reaction of trans-[Au(NH3)2Cl2]+ with s4UMP is approximately the same as with d(s4U). Thus, the electrostatic outer-sphere interaction with a single phosphate group adjacent to the kinetically preferred binding site is not sufficient to induce a reactivity that significantly exceeds that of direct interaction between the thione and the rapidly reacting gold(III) centre. In contrast, reaction of trans-[Au(CN)2Cl2]– with s4UMP is significantly slower than with d(s4U), most likely due to the combined effect of electrostatic repulsion and steric blocking.
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