Рад у часопису

објављена верзија

енглески

Aleksandar M. Mijatović, Ratomir M. Jelić, Jovana Bogojeski, Živadin D. Bugarčić, Biljana Petrović

Kinetics, mechanism, and equilibrium studies of the reactions between a ruthenium(II) complex and some nitrogen- and sulfur-donor nucleophiles

Monatshefte für Chemie - Chemical Monthly

Springer Science and Business Media LLC

2013

Kinetika i mehanizam reakcija supstitucije između [Ru(trpi)(bpi)Cl]+ sa nukleofilima gvanozin-5′-monofosfatom, L-histidinom, tioureom i dimetilsulfoksidom proučavani su spektrofotometrijski u 0,1 M NaClO4 na 310 K. Red reaktivnosti za odabrane ligande je: tiourea > gvanozin-5′-monofosfat > L-histidin > DMSO. Ovaj red je povezan sa elektronskim, strukturnim i hemijskim karakteristikama kompleksa i nukleofila. Reakcija supstitucije sa tioureom je proučavana na tri različite temperature (288, 298 i 310 K). Negativna entropija aktivacije DS = potvrđuje asocijativni način aktivacije. Formiranje kompleksa [Ru(trpi)(bpi)H2O]2+ sa ligandima gvanozin-5′-monofosfat i L-histidin je takođe ispitivano potenciometrijom i spektrofotometrijom. Određene su stehiometrija i konstante stabilnosti vrsta koje se formiraju u ovim sistemima. Dijagram raspodele koncentracije različitih kompleksa je procenjen kao funkcija pH. Upoređujući izračunate vrednosti za logb, utvrdili smo da je proizvod sa nukleotidom stabilniji od proizvoda sa L-histidinom.

Kinetics and mechanism of the substitution reactions between [Ru(trpy)(bpy)Cl]+ with nucleophiles guanosine-5′-monophosphate, L-histidine, thiourea, and dimethylsulfoxide were studied spectrophotometrically in 0.1 M NaClO4 at 310 K. The observed order of reactivity for selected ligands is: thiourea > guanosine-5′-monophosphate > L-histidine > DMSO. This order is associated with the electronic, structural, and chemical characteristics of complex and nucleophiles. The substitution reaction with thiourea was studied at three different temperatures (288, 298, and 310 K). Negative entropy of activation ΔS ≠ confirms the associative mode of activation. The complex formation of [Ru(trpy)(bpy)H2O]2+ with ligands guanosine-5′-monophosphate and L-histidine was investigated by potentiometry and spectrophotometry as well. The stoichiometry and stability constants of the species formed in these systems were determined. The concentration distribution diagram of the various complexes has been evaluated as a function of pH. Comparing the calculated values for logβ, we determined that the product with nucleotide is more stable than the product with L-histidine.

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10.1007/s00706-013-1044-1

0026-9247

Kinetika, Ravnoteža, Ru(II), L-Histidin, Guanozin-5' -monofosfat, Dimetilsulfoksid, Tiourea

Kinetics, Equilibrium, Ru(II), L-Histidine, Guanosine-5' -monophosphate, Dimethylsulfoxide, Thiourea

http://link.springer.com/content/pdf/10.1007/s00706-013-1044-1.pdf

M20

М22

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

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