Kinetics and Mechanism of Palladium(II)-Catalyzed Oxidation of Inositol by Hexachloroplatinate(IV) in Perchlorate Solutions

Ahmed Fawzy; Ishaq A. Zaafarany; Khalid S. Khairou; Sheigha S. Ashour; Naeema Yarkandi

doi:doi:10.11648/j.ajac.20160405.15

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Kinetics and Mechanism of Palladium(II)-Catalyzed Oxidation of Inositol by Hexachloroplatinate(IV) in Perchlorate Solutions

Ahmed Fawzy, Ishaq A. Zaafarany, Khalid S. Khairou, Sheigha S. Ashour, Naeema Yarkandi

Published in American Journal of Applied Chemistry (Volume 4, Issue 5)

Received: 29 August 2016 Accepted: 8 September 2016 Published: 24 September 2016

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Abstract

Oxidation of inositol (INOS) by hexachloroplatinate(IV) complex (HCP) in perchlorate solutions in the presence of palladium(II) catalyst was studied spectrophotometrically. The reaction rate was very slow in the absence of the catalyst. The reaction exhibited a first order dependence on [HCP], and fractional-first order dependences with respect to [INOS], [H+] and [Pd(II)]. Increasing ionic strength and dielectric constant was found to increase the oxidation rate. A probable oxidation mechanism has been suggested and the rate-law expression has been derived. Both spectral and kinetic evidences revealed formation of a 1:1 intermediate complex between INOS and Pd(II) prior to the rate-controlling step. The final oxidation product of inositol was identified by both spectral and chemical analyses as the corresponding monoketone derivative, namely inosose. The activation parameters of the second order rate constant were evaluated and discussed.

Published in	American Journal of Applied Chemistry (Volume 4, Issue 5)
DOI	10.11648/j.ajac.20160405.15
Page(s)	185-191
Creative Commons	This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.
Copyright	Copyright © The Author(s), 2016. Published by Science Publishing Group

Keywords

Inositol, Hexachloroplatinate(IV), Oxidation, Palladium(II), Kinetics, Mechanism

References

[1]	Keage MC, Kelland MJ, Neidles LR, Warning MJ, ed. (1993) Molecular Aspects of Anticover Drug DNA Interactions, vol. 1, CRC Press, New York, NY, USA.
[2]	Lemma K, Sargeson A, Elding LI (2000) Kinetics and mechanism for reduction of oral anticancer platinum(IV) dicarboxylate compounds by L-ascorbate ions. J. Chem. Soc. Dalton Trans. 7: 1167-1172.
[3]	Lemma K, Shi T, Elding LI (2000) Kinetics and mechanism for reduction of the anticancer prodrugtrans, trans, trans-[PtCl₂ (OH)₂(c-C₆H₁₁NH₂)(NH₃)] (JM335) by thiols. Inorg. Chem. 39: 1728–1734.
[4]	Weiss RP, Christian MC (1993) Newcisplatin analogues in development. A review. Drugs 46: 360-377.
[5]	Beattie K, Basolo F (1967) Reduction of some platinum(IV) complexes with tris(bipyridine) chromium(II) ion. Inorg. Chem. 6: 2069-2073.
[6]	Beattie K, Basolo F (1971) Two-electron inner-sphere reduction of chloropentaammine-platinum(IV) ion by aquo-chromium(II) ion. Inorg. Chem. 10: 486-491.
[7]	Moodley KG, Nicol MJ (1977) Kinetics of the reduction of platinum(IV) by tin(II) and copper(I) in aqueous chloride solutions. J. Chem. Soc. Dalton Trans. 239-243.
[8]	Pal B, Sen Gupta KK (2000) Kinetics and mechanism of hexachloroplatinate(IV) reduction by some neutralized alpha-hydroxy acids in a carbonate-hydrogen carbonate buffer medium, Bull. Chem. Soc. Jpn. 73: 553-560.
[9]	Fawzy A (2014) Influence of copper(II) catalyst on the oxidation of L-histidine by platinum(IV) in alkaline medium: a kinetic and mechanistic study. Transition Met. Chem. 39: 567-576.
[10]	Fawzy A (2015) Kinetics and mechanistic approach to the oxidative behavior of biological anticancer platinum(IV) complex towards L-asparagine in acid medium and the effect of copper(II) catalyst. Int. J. Chem. Kinet. 47: 1-12.
[11]	Fawzy A, Asghar BH (2015) Kinetics and mechanism of uncatalyzed and silver(I)-catalyzed oxidation of L-histidine by hexachloroplatinate(IV) in acid medium. Transition Met. Chem. 40: 287-295.
[12]	Asghar BH, Altass HM, Fawzy A (2015) Transition metal ions-catalyzed oxidation of L-asparagine by platinum(IV) in acid medium: a kinetic and mechanistic study. Transition Met. Chem. 40: 587–594.
[13]	Fawzy A, Zaafarany IA (2015) Kinetic and mechanistic investigation on the zirconium(IV)-catalyzed oxidation of L-histidine by hexachloroplatinate(IV) in acid medium. Chem. Sci. Rev. Lett. 4: 608-618.
[14]	Fawzy A, Zaafarany IA (2015) Mechanistic investigation of copper(II)-catalyzed oxidation of L-asparagine by hexachloroplatinate(IV) in aqueous alkaline medium: a kinetic approach. J. Multidisc. Eng. Sci. Technol. 2: 1038-1045.
[15]	Asghar BH, Altass HM, Fawzy A (2016) Silver(I)-catalysis of oxidative deamination and decarboxylation of L-asparagine and L-histidine by platinum(IV) in perchloric acid solutions: a comparative kinetics study. J. Env. Chem. Eng.4:617-623.
[16]	Michell RH (2007) Evolution of the diverse biological roles of inositols. Biochem. Soc. Symp. 74: 223-246.
[17]	Shen X, Xiao H, Ranallo R, Wu WH, Wu C (2003) Modulation of ATP-dependent chromatin-remodeling complexes by inositol polyphosphates. Science 299: 112-114.
[18]	Rapiejko PJ, Northup JK, Evans T, Brown JE, Malbon CC (1986) G proteins of fat cells role in hormonal regulation of intracellular inositol 1,4,5-trisphosphate. Biochem. J. 240:35-40
[19]	Larner J (2002) D-chiro-inositol –its functional role in insulin action and its deficit in insulin resistance. Int. J. Exp. Diabetes Res.3:47-60.
[20]	Kumar YL, Nadh RV, Radhakrisinami PS (2012) Kinetics of oxidation of myo-inositol by potassium periodate in alkaline medium. Asian J. Chem. 24:5869-5872.
[21]	Nayak GT, Hadmani CC, Harihar AL (2015) Kinetic and mechanistic investigations of oxidation of myo-inositol by diperiodatocuprate(III) in aqueous alkaline medium. Chem. Sci. Trans. 4:199-207.
[22]	Nayak GT, Hadmani CC, Harihar AL (2014) Oxidation of myo-inositol by alkaline permanganate and the effect of alkali metal ion catalysts: kinetic and mechanistic approach. Know Res. 1:33-39.
[23]	Kumar A, Rain M (1974) Mechanism of oxidation of cyclohexanehexol (inositol) by quinquevalentvanadium. Int J Chem. Kinet. 6:15-28.
[24]	Santoro M, Caffaratti E, Salas-Peregrin GM, Korecz L, Rockenbauer A, Sala LF, Signorella F (2007) Kinetics and mechanism of the chromic oxidation of myo-inositol. Polyhedron 26:169–177.
[25]	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.
[26]	Sumathi T, Sundaram PS, Chandramohan G (2011) A kinetic and mechanistic study on the silver(I)-catalyzed oxidation of L-alanine by cerium (IV) in sulfuric acid medium. Arab J. Chem. 4: 427–435.
[27]	Devra V, Jain S, Sharma PD (1994) Kinetics and mechanism of oxidation of glycine, alanine, and threonine by fluoride coordinated bismuth(V) in aqueous HClO4–HF medium. Int. J. Chem. Kinet. 26: 577–585.
[28]	Fawzy A, Ashour SS, Musleh MA, Hassan RM, Asghar BH (2015) Kinetics and mechanistic approach to the chromic acid oxidation of L-tryptophan with a spectral detection of chromium(III) product. J. Saudi Chem. Soc. in press.
[29]	Senagar SKS, Yadav BS (1988) Kinetics and mechanism of copper(II)–catalyzed oxidation of asparagine by sodium N-chloro-p-toluene sulphonamide in alkaline media. J. Indian Chem. Soc. 65: 88–90.
[30]	Asghar BH, Altass HM, Fawzy A (2015) Copper(II) catalysis for oxidation of L-tryptophan by hexacyanoferrate(III) in alkaline medium: a kinetic and mechanistic approach. J. Saudi. Chem. Soc. in press.
[31]	Fawzy A (2015) Palladium(II)-catalyzed oxidation of L-tryptophan by hexacyanoferrate(III) in perchloric acid medium: a kinetic and mechanistic approach. J. Chem. Sci. In press.
[32]	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.
[33]	Tsuji J (2004) Palladium reagents and catalysis - New Perspective for the 21^st century; 2^nded, John Wiley & Sons Ltd: Chichester.
[34]	Garrett CE, Prasad K (2004) The art of meeting palladium specifications in active pharmaceutical ingredients produced by Pd-catalyzed reactions. Adv. Synth. Catal. 346: 889-896.
[35]	Zapf A, Beller M (2002) Fine chemical synthesis with homogeneous palladium catalysts: examples, status and trends. Top. Catal. 19: 101-109.
[36]	Chimatadar SA, Koujalagi SB, Nandibewoor ST (2002) Kinetics of palladium(II) catalyzed oxidation of mercury(I) by iron(III)- 2,2′-bipyridyl complex. Indian J. Chem. 41A:316-320.
[37]	Singh AK, Jaiswal J, Singh RA, Singh K (2009) Mechanism of palladium(II) catalysis in cerium(IV) oxidation of amines in acidic medium. Asian J. Chem. 21:858-862.
[38]	Gligorich KM, Sigman MS (2009) Recent advancements and challenges of palladium(II)-catalyzed oxidation reactions with molecular oxygen as the sole oxidant. Chem. Commun.3854-3862.
[39]	Georgieva M, Andonovski B (2003) Determination of platinum(IV) by UV spectrophotometry. Anal. Bioanal. Chem. 375: 836-839.
[40]	Vogel AI (1973) Text book of practical organic chemistry, 3^rd ed., ELBS Longman, London, pp. 332 and 679.
[41]	Feigl F (1975) Spot tests in organic analysis, 195 pp. Elsevier, New York.
[42]	Amis ES (1966) Solvent effect on reaction rates and mechanism, Academic Press, New York, pp. 28; Frost AA, Person RG (1970) Kinetics and mechanism, Wiley Eastern, New Delhi, pp. 147
[43]	Laidler K (1965) Chemical Kinetics. McGraw-Hill, New York.
[44]	Weissberger A (1974) In Investigation of rates and mechanism of reactions in techniques of chemistry, John Wiley & Sons (New York: Interscience Publication) pp. 421.

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APA Style

Ahmed Fawzy, Ishaq A. Zaafarany, Khalid S. Khairou, Sheigha S. Ashour, Naeema Yarkandi. (2016). Kinetics and Mechanism of Palladium(II)-Catalyzed Oxidation of Inositol by Hexachloroplatinate(IV) in Perchlorate Solutions. American Journal of Applied Chemistry, 4(5), 185-191. https://doi.org/10.11648/j.ajac.20160405.15

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ACS Style

Ahmed Fawzy; Ishaq A. Zaafarany; Khalid S. Khairou; Sheigha S. Ashour; Naeema Yarkandi. Kinetics and Mechanism of Palladium(II)-Catalyzed Oxidation of Inositol by Hexachloroplatinate(IV) in Perchlorate Solutions. Am. J. Appl. Chem. 2016, 4(5), 185-191. doi: 10.11648/j.ajac.20160405.15

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AMA Style

Ahmed Fawzy, Ishaq A. Zaafarany, Khalid S. Khairou, Sheigha S. Ashour, Naeema Yarkandi. Kinetics and Mechanism of Palladium(II)-Catalyzed Oxidation of Inositol by Hexachloroplatinate(IV) in Perchlorate Solutions. Am J Appl Chem. 2016;4(5):185-191. doi: 10.11648/j.ajac.20160405.15

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@article{10.11648/j.ajac.20160405.15,
  author = {Ahmed Fawzy and Ishaq A. Zaafarany and Khalid S. Khairou and Sheigha S. Ashour and Naeema Yarkandi},
  title = {Kinetics and Mechanism of Palladium(II)-Catalyzed Oxidation of Inositol by Hexachloroplatinate(IV) in Perchlorate Solutions},
  journal = {American Journal of Applied Chemistry},
  volume = {4},
  number = {5},
  pages = {185-191},
  doi = {10.11648/j.ajac.20160405.15},
  url = {https://doi.org/10.11648/j.ajac.20160405.15},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajac.20160405.15},
  abstract = {Oxidation of inositol (INOS) by hexachloroplatinate(IV) complex (HCP) in perchlorate solutions in the presence of palladium(II) catalyst was studied spectrophotometrically. The reaction rate was very slow in the absence of the catalyst. The reaction exhibited a first order dependence on [HCP], and fractional-first order dependences with respect to [INOS], [H+] and [Pd(II)]. Increasing ionic strength and dielectric constant was found to increase the oxidation rate. A probable oxidation mechanism has been suggested and the rate-law expression has been derived. Both spectral and kinetic evidences revealed formation of a 1:1 intermediate complex between INOS and Pd(II) prior to the rate-controlling step. The final oxidation product of inositol was identified by both spectral and chemical analyses as the corresponding monoketone derivative, namely inosose. The activation parameters of the second order rate constant were evaluated and discussed.},
 year = {2016}
}

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TY  - JOUR
T1  - Kinetics and Mechanism of Palladium(II)-Catalyzed Oxidation of Inositol by Hexachloroplatinate(IV) in Perchlorate Solutions
AU  - Ahmed Fawzy
AU  - Ishaq A. Zaafarany
AU  - Khalid S. Khairou
AU  - Sheigha S. Ashour
AU  - Naeema Yarkandi
Y1  - 2016/09/24
PY  - 2016
N1  - https://doi.org/10.11648/j.ajac.20160405.15
DO  - 10.11648/j.ajac.20160405.15
T2  - American Journal of Applied Chemistry
JF  - American Journal of Applied Chemistry
JO  - American Journal of Applied Chemistry
SP  - 185
EP  - 191
PB  - Science Publishing Group
SN  - 2330-8745
UR  - https://doi.org/10.11648/j.ajac.20160405.15
AB  - Oxidation of inositol (INOS) by hexachloroplatinate(IV) complex (HCP) in perchlorate solutions in the presence of palladium(II) catalyst was studied spectrophotometrically. The reaction rate was very slow in the absence of the catalyst. The reaction exhibited a first order dependence on [HCP], and fractional-first order dependences with respect to [INOS], [H+] and [Pd(II)]. Increasing ionic strength and dielectric constant was found to increase the oxidation rate. A probable oxidation mechanism has been suggested and the rate-law expression has been derived. Both spectral and kinetic evidences revealed formation of a 1:1 intermediate complex between INOS and Pd(II) prior to the rate-controlling step. The final oxidation product of inositol was identified by both spectral and chemical analyses as the corresponding monoketone derivative, namely inosose. The activation parameters of the second order rate constant were evaluated and discussed.
VL  - 4
IS  - 5
ER  -

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Author Information

Ahmed Fawzy

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
Khalid S. Khairou

Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Sheigha S. Ashour

Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Naeema Yarkandi

Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia

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APA Style

Ahmed Fawzy, Ishaq A. Zaafarany, Khalid S. Khairou, Sheigha S. Ashour, Naeema Yarkandi. (2016). Kinetics and Mechanism of Palladium(II)-Catalyzed Oxidation of Inositol by Hexachloroplatinate(IV) in Perchlorate Solutions. American Journal of Applied Chemistry, 4(5), 185-191. https://doi.org/10.11648/j.ajac.20160405.15

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ACS Style

Ahmed Fawzy; Ishaq A. Zaafarany; Khalid S. Khairou; Sheigha S. Ashour; Naeema Yarkandi. Kinetics and Mechanism of Palladium(II)-Catalyzed Oxidation of Inositol by Hexachloroplatinate(IV) in Perchlorate Solutions. Am. J. Appl. Chem. 2016, 4(5), 185-191. doi: 10.11648/j.ajac.20160405.15

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AMA Style

Ahmed Fawzy, Ishaq A. Zaafarany, Khalid S. Khairou, Sheigha S. Ashour, Naeema Yarkandi. Kinetics and Mechanism of Palladium(II)-Catalyzed Oxidation of Inositol by Hexachloroplatinate(IV) in Perchlorate Solutions. Am J Appl Chem. 2016;4(5):185-191. doi: 10.11648/j.ajac.20160405.15

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@article{10.11648/j.ajac.20160405.15,
  author = {Ahmed Fawzy and Ishaq A. Zaafarany and Khalid S. Khairou and Sheigha S. Ashour and Naeema Yarkandi},
  title = {Kinetics and Mechanism of Palladium(II)-Catalyzed Oxidation of Inositol by Hexachloroplatinate(IV) in Perchlorate Solutions},
  journal = {American Journal of Applied Chemistry},
  volume = {4},
  number = {5},
  pages = {185-191},
  doi = {10.11648/j.ajac.20160405.15},
  url = {https://doi.org/10.11648/j.ajac.20160405.15},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajac.20160405.15},
  abstract = {Oxidation of inositol (INOS) by hexachloroplatinate(IV) complex (HCP) in perchlorate solutions in the presence of palladium(II) catalyst was studied spectrophotometrically. The reaction rate was very slow in the absence of the catalyst. The reaction exhibited a first order dependence on [HCP], and fractional-first order dependences with respect to [INOS], [H+] and [Pd(II)]. Increasing ionic strength and dielectric constant was found to increase the oxidation rate. A probable oxidation mechanism has been suggested and the rate-law expression has been derived. Both spectral and kinetic evidences revealed formation of a 1:1 intermediate complex between INOS and Pd(II) prior to the rate-controlling step. The final oxidation product of inositol was identified by both spectral and chemical analyses as the corresponding monoketone derivative, namely inosose. The activation parameters of the second order rate constant were evaluated and discussed.},
 year = {2016}
}

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TY  - JOUR
T1  - Kinetics and Mechanism of Palladium(II)-Catalyzed Oxidation of Inositol by Hexachloroplatinate(IV) in Perchlorate Solutions
AU  - Ahmed Fawzy
AU  - Ishaq A. Zaafarany
AU  - Khalid S. Khairou
AU  - Sheigha S. Ashour
AU  - Naeema Yarkandi
Y1  - 2016/09/24
PY  - 2016
N1  - https://doi.org/10.11648/j.ajac.20160405.15
DO  - 10.11648/j.ajac.20160405.15
T2  - American Journal of Applied Chemistry
JF  - American Journal of Applied Chemistry
JO  - American Journal of Applied Chemistry
SP  - 185
EP  - 191
PB  - Science Publishing Group
SN  - 2330-8745
UR  - https://doi.org/10.11648/j.ajac.20160405.15
AB  - Oxidation of inositol (INOS) by hexachloroplatinate(IV) complex (HCP) in perchlorate solutions in the presence of palladium(II) catalyst was studied spectrophotometrically. The reaction rate was very slow in the absence of the catalyst. The reaction exhibited a first order dependence on [HCP], and fractional-first order dependences with respect to [INOS], [H+] and [Pd(II)]. Increasing ionic strength and dielectric constant was found to increase the oxidation rate. A probable oxidation mechanism has been suggested and the rate-law expression has been derived. Both spectral and kinetic evidences revealed formation of a 1:1 intermediate complex between INOS and Pd(II) prior to the rate-controlling step. The final oxidation product of inositol was identified by both spectral and chemical analyses as the corresponding monoketone derivative, namely inosose. The activation parameters of the second order rate constant were evaluated and discussed.
VL  - 4
IS  - 5
ER  -

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