Influence of the decomposition of Tris(2,2-bipyridine)iron(II) and (III) on the reduction of Tris(2,2-bipyridine)iron(III) by hydrazine in aqueous acidic medium: a kinetic study

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• 作者：Ali A. G. A. Al Mahdi ; Mohammed A. Hussein ; Eleanor Fourie…
• 刊名：Transition Metal Chemistry
• 出版年：2016
• 出版时间：February 2016
• 年：2016
• 卷：41
• 期：1
• 页码：25-34
• 全文大小：950 KB
• 参考文献：1.Barchardt D, Pool K, Wherland S (1982) Inorg Chem 21:93CrossRef
  2.Nielsen R, Wherland S (1984) Inorg Chem 23:1338CrossRef
  3.Pelizzetti E, Pramauro E, Blandamer MJ, Burgess J, Gosal N (1985) Inorg Chim Acta 102:163CrossRef
  4.Cotton FA, Wilkinson G (1967) Advanced inorganic chemistry. Wiley-Interscience, New York, p 208
  5.Leipoldt JG, Bok LDC, Van Wyk AJ, Dennis CR (1977) Reac Kinet Catal Lett 6:467CrossRef
  6.Dennis CR, Van Wyk AJ, Basson SS, Leipoldt JG (1987) Inorg Chem 26:270CrossRef
  7.Stanbury DM (1984) Inorg Chem 23:2879CrossRef
  8.Han J-Y, Swarts JC, Sykes AG (1996) Inorg Chem 35:4629CrossRef
  9.Al Mahdi AAGA, Hussein MA, Joubert CC, Swarts JC, Dennis CR (2014) Polyhedron 81:409CrossRef
  10.Adams JQ, Thomas JR (1963) J Chem Phys 39:1904CrossRef
  11.Falle RH (1968) Can J Chem 46:1703CrossRef
  12.Stanbury DM (1998) In: Karlin KD (ed) Progress in Inorg Chem, vol 47. Wiley, New York, pp 551–561
  13.Schilt AA (1963) Anal Chem 35:1599CrossRef
  14.Nord G, Wernberg O (1972) J Chem Soc Dalton 866
  15.Nord G, Wernberg O (1975) J Chem Soc Dalton 845
  16.Wangila GW, Jordan RB (2005) Inorg Chim Acta 358:2804CrossRef
  17.Ogunlusi GO, Ige J, Oyetunji OA (2013) Trans Met Chem 38:45CrossRef
  18.Basolo F, Hayes JC, Neuman HM (1954) J Am Chem Soc 76:3807CrossRef
  19.Tachiyashiki S, Yamatera H (1984) Bull Chem Soc Jpn 57:1070CrossRef
  20.Fries J, Getro H (1977) Organic reagents for trace analysis. E Merck, Darmstad
  21.Hara Y, Fujimoto K, Mayama H (2014) J Phys Chem B 118:608CrossRef
  22.Balakumar P, Balakumar S, Subramaniam P (2012) Reac Kinet Mech Cat 107:257CrossRef
  23.Kolthoff JM, Belcher R (1987) Volumetric analysis, vol 3. Interscience Inc, New York
  24.Vogel AI (1961) Quantitative inorganic analysis, 3rd edn. Longman, London
  25.Beller G, Lente G, Fabian I (2010) Inorg Chem 49:3698CrossRef
  26.Lente G, Fabian I, Poe AJ (2005) N J Chem 29:759CrossRef
  27.Scientist 3.0 software, Micromath (2012) Saint Louis, Missouri, USA
  28.Wilkens RG (1991) The study of kinetics and mechanism of reactions of transition metal complexes, 2nd edn. Allyn and Bacon, BostonCrossRef
  29.Swarts JC, Aquino MAS, Han J-Y, Lam KY, Sykes AG (1995) Biochim et Biophys Acta 1247:215CrossRef
  30.Zhongjiang J, Margerum DW (1999) Inorg Chem 38:5374CrossRef
  31.Smith RM, Martell E (1976) Critical stability constants. Plenum, New YorkCrossRef
  32.Mezek SP, Tateishi M, MacFarlane R, Bartels DM (1996) J Chem Soc, Faraday Trans 92:2451
  33.Back RA (1984) Rev Chem Intermed 5:293CrossRef
  34.Goldstein S, Meyerstein D, Van Eldik R, Czapski G (1997) J Phys Chem A 101:7114CrossRef
  
• 作者单位：Ali A. G. A. Al Mahdi (1) (2)
  Mohammed A. Hussein (1) (2)
  Eleanor Fourie (1)
  Jannie C. Swarts (1)
  C. Robert Dennis (1)
  
  1. Chemistry Department, University of the Free State, P.O. Box 339, Bloemfontein, 9300, Republic of South Africa
  2. Chemistry Department, University of Khartoum, Khartoum, Sudan
  
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Catalysis
  Physical Chemistry
  Inorganic Chemistry
  
• 出版者：Springer Netherlands
• ISSN：1572-901X

文摘

The reduction of tris(2,2-bipyridine)iron(III) by hydrazine in aqueous acidic medium exhibits first-order kinetics in both \( {\text{Fe}}^{\text{III}} \left( {\text{bipy}} \right)_{3}^{3 + } \) and hydrazine. Saturation kinetics, consistent with reactant association prior to the redox step, has been observed. Because this reaction takes place while both the reactant, \( {\text{Fe}}^{\text{III}} \left( {\text{bipy}} \right)_{3}^{3 + } \), and the reduced product, \( {\text{Fe}}^{\text{II}} \left( {\text{bipy}} \right)_{3}^{2 + } \), decompose, a study of the irreversible decomposition of \( {\text{Fe}}^{\text{II}} \left( {\text{bipy}} \right)_{3}^{2 + } \) and \( {\text{Fe}}^{\text{III}} \left( {\text{bipy}} \right)_{3}^{3 + } \) has also been performed. The decomposition rate of the \( {\text{Fe}}^{\text{II}} \left( {\text{bipy}} \right)_{3}^{2 + } \) and \( {\text{Fe}}^{\text{III}} \left( {\text{bipy}} \right)_{3}^{3 + } \) species is, respectively, at least ca. 50- and ca. 40-fold slower than the N₂H₄-induced reduction of tris(2,2-bipyridine)iron(III) (k ₂ = 2.1 M−1s−1 at [H+] = 0.0273 M, µ = 1.0 M and T = 25.0 ± 0.1 °C) under comparable conditions. An increase in [H+] of the reaction medium has a decreasing effect on the rate of the \( {\text{Fe}}^{\text{III}} \left( {\text{bipy}} \right)_{3}^{3 + } \) reduction with hydrazine. A kinetically determined K _a1 value for the dissociation of \( {\text{N}}_{2} {\text{H}}_{6}^{2 + } \) has been obtained as K _a1 = 0.16 ± 0.01 M (pK _a1 = 0.80) at µ = 1.0 M. \( {\text{N}}_{2} {\text{H}}_{5}^{ + } \) was found to be the more reactive hydrazine species in aqueous acidic medium. Activation parameters, applicable to the utilized experimental conditions for the hydrazine-induced reduction of \( {\text{Fe}}^{\text{III}} \left( {\text{bipy}} \right)_{3}^{3 + } \) , have been determined as ΔH ‡ = 54 ± 2 kJ mol−1 and ΔS ‡ = −102 ± 6 J K−1 mol−1.