Kinetics and Mechanism of Electron Transfer to Manganese(VII) by Fluorene and Its Halogenated Derivatives in Neutral Organic Medium
Volume 4, Issue 4, August 2016, Pages: 38-44
Received: Sep. 10, 2016;
Accepted: Oct. 10, 2016;
Published: Nov. 1, 2016
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Ahmed Fawzy, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia; Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt
Rabab J. Jassas, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Saleh A. Ahmed, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia; Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt
Rami J. Obaid, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Ishaq A. Zaafarany, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
The kinetics of oxidation of fluorene (Fl) and its halogenated derivatives, namely, 2,7-dichlorofluorene (Fl-Cl), 2,7-dibromofluorene (Fl-Br) and 2,7-diiodofluorene (Fl-I), by permanganate ion in neutral organic medium in the presence of phosphate buffer solution has been investigated at a constant temperature of 25°C. The progresses of the reactions were followed spectrophotometrically. The stoichiometry of the reactions was found to be 3:4 (fluorene: permanganate). The oxidation reactions exhibited a first order dependence in [permanganate] and less than unit order dependences with respect to fluorenes concentrations. Under comparable experimental conditions, the order of the oxidation rate of the fluorene derivatives was: Fl-Cl > Fl > Fl-I > Fl-Br. The final oxidation products of fluorene derivatives were identified by GC/MS, FT-IR and chemical tools as the corresponding ketones (9H-fluorenone derivatives). The proposed oxidation mechanism involves formation of 1:1 intermediate complexes between fluorene derivatives and permanganate ion in pre-equilibrium step. The rate-law expression was deduced. The reactions constants involved in the different steps of the mechanism were evaluated. The activation parameters associated with the second order rate constants were calculated and discussed.
Rabab J. Jassas,
Saleh A. Ahmed,
Rami J. Obaid,
Ishaq A. Zaafarany,
Kinetics and Mechanism of Electron Transfer to Manganese(VII) by Fluorene and Its Halogenated Derivatives in Neutral Organic Medium, Modern Chemistry.
Vol. 4, No. 4,
2016, pp. 38-44.
Thormann T, Rogojerov M, Jordanov B, Thulstrup EW (1999) Vibrational polarization spectroscopy of fluorene: alignment in stretched polymers and nematic liquid crystals, J. Mol. Str. 509:93-99.
Environmental contaminants encyclopedia fluorene entry July 1, 1997.
Li X, Lü H, Wang S, Guo J, Li J (2011) Sensitizers of dye-sensitized solar cells, Prog. Chem., 23:569-588.
Ma Z, Ding J, Cheng Y, Xie Z, Wang L, Jing X, Wang F (2011) Synthesis and characterization of red light-emitting electrophosphorescent polymers with different triplet energy main chain, Polymer, 52:2189-2197.
Wang HY, Qian Q, Lin KH, Peng B, Huang W, Liu F, Wei W (2012) Stable and good color purity white light-emitting devices based on random fluorene/spirofluorene copolymers doped with iridium complex, J. Polym. Sci. B, 50:180-188.
Yang XH, Wu FI, Neher D, Chien CH, Shu CF (2008) Polyfluorene-based semiconductors combined with various periodic table elements for organic electronics, Chem. Mater., 20:1629-1635.
Kucherak OA, Didier P, Mély Y, Klymchenko AS (2010) Fluorene analogues of prodan with superior fluorescence brightness and solvatochromism, J. Phys. Chem. Lett., 1:616-620.
Cheng YJ, Yang SH, Hsu CS (2009) Synthesis of conjugated polymers for organic solar cell applications, Chem. Rev., 109: 5868-5923.
Xing X, Zhang L, Liu R, Li S, Qu B, Chen Z (2012) A deep-blue emitter with electron transporting property to improve charge balance for organic light-emitting device, ACS Appl. Mater. Interf., 4:2877-2883.
Pina J de, Melo JSS, Egkert A, Scherf U (2015) Unusual photophysical properties of conjugated, alternating indigo–fluorene copolymers, J. Mater. Chem. A, 3:6373-6381.
Fromm R, Ahmed SA, Hartmann Th, Huch V, Abdel-Wahab AA, Dürr A (2001) Eur. J. Org. Chem., 21:4077-4085.
Ahmed SA, Abdel-Wahab AA, Dürr H (2003) CRC Handbook of organic photochemistry and photobiology, Horspool WM, Lenci F edn, CRC press, New York, 2nd edn, Chapter 96, p 1.
Ahmed SA, Hartmann Th, Dürr H (2008) Photochromism of dihydroindolizines: Part VIII. First holographic image recording based on di- & tetrahydroindolizines photochromes, J. Photochem. Photobiol., 200: 50-56.
Ahmed SA, Pozzo JL (2008) Photochromism of dihydroindolizines Part IX. First attempts towards efficient self-assembling organogelators based on photochromicdihydroindolizines and N-acyl-I,-amino acid units, J. Photochem. Photobiol., 200: 57-67.
Fawzy A, Ashour SS, Musleh MA (2014) Base-catalyzed oxidation of L-asparagine by alkaline permanganate and the effect of alkali-metal ion catalysts: kinetics and mechanistic approach, React. Kinet. Mech. Catal. 111:443-460.
Fawzy A, Shaaban MR (2014) Kinetic and mechanistic investigations on the oxidation of N’-heteroaryl unsymmetrical formamidines by permanganate in aqueous alkaline medium. Transition Met. Chem. 39: 379-386.
Fawzy A, Zaafarany IA, Alfahemi J, Tirkistani FA (2015) Base-catalyzed oxidation of aminotriazole derivative by permanganate ion in aqueous alkaline medium: a kinetic study. Int. J. Inn. Res. Sci. Eng. Tech., 4: 6802-6814.
Asghar BH, Fawzy A (2016) Kinetic, mechanistic, and spectroscopic studies of permanganate oxidation of azinylformamidines in acidic medium, with autocatalytic behavior of manganese(II). J. Saudi Chem. Soc., 20: 561–569.
Fawzy A, Ashour SS, Musleh MA (2014) Kinetics and mechanism of oxidation of L-histidine by permanganate ions in sulfuric acid medium. Int. J. Chem. Kinet., 46: 370-381.
Ahmed GA, Fawzy A, Hassan RM (2007) Spectrophotometric evidence for the formation of short-lived hypomanganate(V) and manganate(VI) transient species during the oxidation of K-carrageenan by alkaline permanganate. Carbohydr. Res., 342: 1382-1386.
Zaafarany IA, Fawzy A, Ahmed GA, Ibrahim SA, Hassan RM, Takagi HD (2010) Further evidence for detection of short-lived transient hypomanganate(V) and manganate(VI) intermediates during oxidation of some sulfated polysaccharides by alkaline permanganate using conventional spectrophotometeric techniques. Carbohydr. Res., 345: 1588-1593.
Hassan RM, Fawzy A, Alarifi A, Ahmed GA, Zaafarany IA, Takagi HD (2011) Base-catalyzed oxidation of some sulfated macromolecules: kinetics and mechanism of formation of intermediate complexes of short-lived manganate (VI) and/or hypomanganate (V) during oxidation of iota- and lambda-carrageenan polysaccharides by alkaline permanganate. J. Mol. Catal. A, 335: 38-45.
Hassan RM, Dahy A, Ibrahim S, Zaafarany IA, Fawzy A (2012) Oxidation of some macromolecules. Kinetics and mechanism of oxidation of methyl cellulose polysaccharide by permanganate ion in acid perchlorate solutions. Ind. Eng. Chem. Res. 51: 5424–5432.
Gardner KA, Kuehnert LL, Mayer JM (1997) Hydrogen atom abstraction by permanganate: oxidations of arylalkanes in organic solvents. Inorg. Chem., 36: 2069-2078.
Kini AK, Farokhi SA, Nandibewoor ST (2002) A comparative study of ruthenium(III) catalysed oxidation of L-leucine and L-isoleucine by alkaline permanganate. A kinetic and mechanistic approach. Transition Met. Chem., 27: 532–540.
Halligudi LL, Desai SM, Mavalangi AK, Nandibewoor ST. (2000) Kinetics of the oxidative degradation of rac-serine by aqueous alkaline permanganate. Monatsh Chem., 131: 321–332.
Verma RS, Reddy JM, Shastry VR. (1974) Kinetic study of homogeneous acid-catalyzed oxidation of certain amino-acids by potassium permanganate in moderately concentrated acidic media. J Chem Soc Perkin Trans., 124: 469–473.
Mohanty B, Behera J, Acharya S, Mohanty P, Pantaik AK. Metal ion catalyzed oxidation of L-lysine by alkaline permanganate Ion-A kinetic and mechanistic approach. Chem. Sci. Trans.. 2013: 2, 51–60.
Cotton FA, Wilkinson G. Advanced Inorganic Chemistry, p 747, John Wiley and Sons, New York (1980).
Ahmed SA (2004) Photochromism of dihydroindolizines. III: synthesis and photochromic behavior of novel photochromic dihydroindolizines incorporating a cholesterol moiety, Monatsh. Chem., 135:1173-1181.
Ahmed SA, Khairou KS, Asghar BH, Muathen HA, Nahas NMA, Al Shreef HF (2014) Photochromism of tetrahydroindolizines. Part XIV: Synthesis of cis-fixed conjugated photochromic pyridazinopyrrolo [1,2-b] isoquinolines incorporating carbon-rich linkers, Tetrahderon Lett., 55: 2190-2197.
Vogel IA. (1978) A Text Book of Quantitative Inorganic Analysis. 4th edn, p 352, ELBS, Longman.
Vogel AI (1973) Text book of practical organic chemistry including quantitative organic analysis, 3rd edn, p 332,. ELBS, Longman.
Feigl F (1975) Spot tests in organic analysis, p 195, Elsevier, New York.
Zimmerman CL. Ph D. Thesis University of Chicago (1949).
Michaelis L, Menten ML (1913) The kinetics of invertase action. Biochem. Z., 49: 333–369.
Hicks KW, Toppen DL, Linck RG (1972) Inner-sphere electron-transfer reactions of vanadium(II) with azidoamine complexes of cobalt(III). Inorg. Chem., 11: 310–315.
Sutin N (1968) Free energies, barriers, and reactivity patterns in oxidation-reduction reactions. Acc. Chem. Res., 1: 225–231.