Kinetics of the reaction of CIS - and trans-PtCl4(NH3)2 Complexes in Aqueous Solution, in the Presence of Ethanol

• Autorzy: Pacławski K. , Luty-Błocho M.

Identyfikatory

DOI

10.15199/67.2016.10.4

Warianty tytułu

EN

Kinetyka reakcji kompleksów CIS- i trans-PtCl4 (NH3)2 w roztworze wodnym, w obecności etanolu

• Języki publikacji: EN

Abstrakty

EN

In this work the kinetic data for the reactions of cis- and trans-PtCl4(NH3)2 complexes with ethanol have been determined. Obtained values of the rate constants determined for different conditions of reactants concentration as well as different temperature indicate that in aqueous solution with pH = 12 the reaction is relatively slow and leads to the cis- and trans-PtCl2(NH3)2 species formation, respectively. Using obtained kinetic results, supported with DFT calculations, the possible mechanism of electron transfer involving the chloride ligand-ethanol bridge formation has been suggested. It was found that the values of enthalpy and entropy of activation correlate well with the difference between the rate constants of both reacting pairs as well as with the difference between HOMO and LUMO energy levels of reagents. From the obtained results, the parallel paths of the cis- and trans-PtCl4(NH3)2 reactions, i.e. reduction and hydrolysis of platinum(IV) complexes, were also suggested.

PL

W artykule przedstawiono dane kinetyczne reakcji kompleksów cis- i trans-PtCIJNHJ2 z etanolem. Wartości stałych szybkości wyznaczone w różnych warunkach stężenia reagentów oraz w różnych temperaturach wskazują, że w roztworach wodnych o pH =12, reakcja jest względnie wolna i prowadzi to utworzenia odpowiednio cis- itrans-PtO2(NHj2. Używając otrzymanych danych kinetycznych oraz obliczeń DFJ, zaproponowano możliwy mechanizm przekazania elektronu obejmujący utworzenie mostka: Ugand chlorkowy-etanol. Wykazano, że wartości entalpii i entropii aktywacji dobrze korelują z różnicą pomiędzy stałymi szybkości reakcji obydwu par reagentów, jak również z różnicą pomiędzy poziomami ener¬getycznymi HOMO i UJMO reagentów. Na podstawie otrzymanych danych oraz dyskusji wyników zaproponowano równoległe ścieżki reakcji cis-i trans-PtCIJNHJj takie jak redukcję i hydrolizę platyny(IV).

Słowa kluczowe

EN

kinetics; mechanism; rate law; cis-PtCl4(NH3)2; trans-PtCl4(NH3)2; platinum (IV)

PL

kinetyka; mechanizm; równanie kinetyczne

• Wydawca: Wydawnictwo SIGMA-NOT
• Czasopismo: Rudy i Metale Nieżelazne Recykling
• Rocznik: 2016
• Tom: R. 61, nr 10
• Strony: 435--443
• Opis fizyczny: Bibliogr. 33 poz., rys., tab.

Twórcy

autor

Pacławski K.

• AGH University of Science and Technology, Faculty of Non-Ferrous Metals, Labolatory of Physico-Chemistry and Metallurgy of Non-Ferrous Metals, 30 Mickiewicz Ave., 30-059 Krakow, Poland

autor

Luty-Błocho M.

• AGH University of Science and Technology, Faculty of Non-Ferrous Metals, Labolatory of Physico-Chemistry and Metallurgy of Non-Ferrous Metals, 30 Mickiewicz Ave., 30-059 Krakow, Poland

Bibliografia

• [1] Akinaga Hiroyuki. 2013. "Recent Advances and Future Prospects in Functional-Oxide Nanoelectronics: The Emerging Materials and Novel Functionalities that are Accelerating Semiconductor Device Research and Development". Japanese Journal of Applied Physics 52: 100001-100012.
• [2] Aldini Giancarlo, Kyung-Jin Yeum, Etsuo Niki, Robert M. Russell. 2010. Biomarkers for Antioxidant Defense and Oxidative Damage. Iowa: John Wiley and Sons.
• [3] Chen Dong-Hwang, Jijunn-Jiun Yeh, Ting-Chia Huang. 1999. "Synthesis of Platinum Ultrafine Particles in AOT Reverse Micelles". Journal of Colloid and Interface Science 215: 159-166.
• [4] Choi Sunhee, Catherine Filotto, Mark Bisanzo, Sarah Delaney, Daniel Lagasse, Jennifer. L. Whitworth, Andrew Jusko, Chengruo Li, Nicole A. Wood, Jennifer Willingham, Amy Schwenker, Kathleen Spaulding. 1998. "Reduction and Anticancer Activity of Platinum(IV) Complexes". Inorganic Chemistry 37 (10): 2500-2504.
• [5] Frisch M. J., G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Jr. Montgomery, J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G.A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox. 2009. "Gaussian 09". Wallingford CT. Gaussian, Inc. http://www.gaussian.com/g_tech/g_ur/m_citation.htm (dostęp: 10.09.2016)
• [6] Gröning Östen, Alan M. Sargeson, Robert J. Deeth, Lars I. Elding. 2000. "Mercury(II) and Square-Planar Platinum(II) Chloro Ammine, Aqua, and Sulfoxide Complexes. Stabilities, Spectra, and Reactivities of Transient Metal-Metal Bonded Platinum-Mercury Adducts". Inorganic Chemistry 39: 4286-4294.
• [7] Hansford G.S., J.T. Chapman. 1992. "Batch and continous biooxidation kinetics of a refractory gold-bearing pyrite concentrate". Minerals Engineering 5: 597-735.
• [8] Hudlický M. 1990. Oxidation in Organic Chemistry. Washington: American Chemical Society.
• [9] Hudlický M. 1996. Reductions in Organic Chemistry. Washington: American Chemical Society.
• [10] Karen Akiya, Michiko T. Sawada, Fumio Tanaka, Noboru Mataga. 1987. "Dynamic of excited flavoproteins - picosecond laser photolysis studies". Photochemistry and Photobiology 45 (1): 49-53.
• [11] Laidler Keith J., M. Christine King. 1983. "Development of transition- state theory". Journal of Physical Chemistry 87: 2657-2664.
• [12] Lemma Kelemu, Alan M. Sargesson, Lars I. Elding. 2000. "Kinetics and mechanism for reduction of oral anticancer platinum(IV) dicarboxylate compounds by L-ascorbate ions". Journal of Chemical Society. Dalton Transactions. 1167-1172.
• [13] Lemma Kelemu, Donald A. House, Negussie Retta, Lars I. Elding. 2002. "Kinetics and mechanism for reduction of halo- and haloam(m) ine platinum(IV) complexes by L-ascorbate". Inorganica Chimica Acta 331 (1): 98-108.
• [14] Lemma Kelemu, Johan Berglund, Nicholas Farrell, Lars I. Elding. 2000. "Kinetics and mechanism for reduction of anticancer-active tetrachloroam(m) ine platinum(IV) compounds by glutathione". Journal of Biological Inorganic Chemistry 5 (3): 300-306.
• [15] Li Y., N. Kawashima, J. Li, A.P. Chandra, Andrea R. Gerson. 2013. "A review of the structure, and fundamental mechanisms and kinetics of the leaching of chalcopyrite". Advances in Colloid Interface Science 197-198: 1-32.
• [16] Lippard Stephan J., Albert Haim. 1983. Mechanisms of Electron Transfer Reactions: The Bridged Activated Complex. W Progress in Inorganic Chemistry. An Appreciation of Henry Taube. New York: John Wiley & Sons, Inc.
• [17] Mailloux Ryan J., Xiaolei Jin, William G. Willmore. 2014. “Redox regulation of mitochondrial function with emphasis on cysteine oxidation reaction". Redox Biology 2: 123-139.
• [18] Miller J.R. 2014. “Lower tunnel barriers". Nature Chemistry 6: 854- 855.
• [19] Mori Hirotoshi, RRyohei Kojima, Yuji Mochizuki, Waka Uenohara, Izumi Umezawa, Nobuyuki Matsushita. 2013. "Importance of spin-orbit coupling effect and solvent effect in electronic transition assignments of PtII complexes: In the case of cis/trans-
• [PtIICl2 (NH3)2]", Journal of Molecular Structure 1035: 218-223.
• [20] Murray Robert K., David A., Kathleen M. Botham, Peter J. Kennelly, Victor W. Rodwell, P. Anhony Weil. 2012. Harper’s Illustrated Biochemistry. Toronto: McGrow Hill.
• [21] Pang S.K., K.C. Yung. 2014. "Prerequisites for achieving gold adsorption by multiwalled carbon nanotubes in gold recovery". Chemical Engineering Science 107: 58-65.
• [22] Piestrzyński Adam. 2007. Monografia KGHM Polska Miedź SA. Lubin: KGHM "Cuprum".
• [23] Pinnel D., R.B. Jordan. 1979. "Kinetics of reduction of cobalt(III) -ammine complexes by dithionite". Inorganic Chemistry 18: 3191- 3194.
• [24] Ramos Yalexmi, Carlos Hernandez, Lidia Asela Fernandez, Mayra Bataller, Eliet Veliz. 2011. "Optimization of HPLC procedure for simultaneous determination of cisplatin and the complex cis, cis, trans-diaminnedichlorodihydroxoplatinum(IV) in aqueous solutions". Quimica Nova 34 (8): 1450-1454.
• [25] Salmony Dorrit, J.K. Whithead. 1954. "Studies on the Oxidation of Gluconate by Animal Tissues". Biochemical Journal 58 (3): 408- 413.
• [26] Sepunaru Lior, Irena Tsimberov, Ludmila Forolov, Chanoch Carmeli, Itai Carmeli, Yossi Rosenwaks. 2009. "Picosecond Electron Transfer from Photosynthetic Reaction Center Protein to GaAs". Nano Letters 9 (7): 2751-2756.
• [27] Shi Tiesheng, Johan Berglund, Lars I. Elding. 1996. "Kinetics and Mechanism for Reduction of trans-Dichlorotetracyanoplatinate( IV) by Thioglycolic Acid, L-Cysteine, DL-Penicillamine, and Glutathione in Aqueous Solution". Inorganic Chemistry 35: 3498-3503.
• [28] Shi Tiesheng, Johan Berglund, Lars I. Elding. 1997. "Reduction of trans-dichloro- and trans-dibromo-tetracyanoplatinate(IV) by L-methionine". Journal Chemical Society. Dalton Transactions. 2073-2078.
• [29] Stetten R. Marjorie, DeWitt Stetten. 1950. "The metabolism of gluconic acid". Journal of Biological Chemistry 187 (1): 241-252.
• [30] Su Ren, Ramchandra Tiruvalam, Andrew J. Logsdail, Qian He, Christopher A. Downing, Mikkel T. Jensen, Nikolaos Dimitratos, Lokesh Kesavan, Peter P. Wells, Ralf Bechstein, Henrik H. Jensen, Stefan Wendt, C. Richard A. Castlow, Christopher J. Kiely, Graham J. Hutchings, Flemming Besenbacher. 2014. "Designer Titania- Supported Au-Pd Nanoparticles for Efficient Photocatalytic Hydrogen Production". ACS Nano 8 (4): 3490-3497.
• [31] Verde Ysmae, Gabriel Alonso-Nunez, Mario Miki-Yoshida, M. Jose- Yacaman,. Victor H. Ramos, Arturo Keer. 2005. "Active area and particle size of Pt particles synthesized from (NH^) 2PtCl6 on a carbon support". Catalysis Today 107-108: 826-830.
• [32] Wondrak T. Georg. 2009. "Redox-Directed Cancer Therapeutics. Molecular Mechanisms and Opportunities". Antioxidants and Redox Signaling 11 (12): 3013-3069.
• [33] Zalewska Marta, Jagoda Trefon, Halina Milnerowicz. 2014. "The role of metallothionein interactions with other proteins". Proteomics 14: 1343-1356.