Spectrophotometric Study of the Interaction Between Aza-15-Crown-5 and Some p-Acceptors in Chloroform Solution

A spectrophotometric study concerning the interaction between A15C5 as n-donor and TCNE, DDQ, TCNQ and bromanil as p -acceptor was been performed in chloroform at 25 °C. The results of TCNE indicate the formation of a 1:1 charge-transfer complex through a nonequilibrium reaction. In the case of DDQ, the formation of 1:2 (A15C5/DDQ) and 1:1 charge-transfer complexes through equilibrium and nonequilibrium reactions is confirmed. The formation constant of the equilibrium step was evaluated from the computer fitting of the absorbance-mole ratio data as logKf = 5.14 \pm 0.09. The [A15C5+ (DDQ)2- ] and [A15C5+DDQ- ] are suggested as the possible 1:2 and 1:1 adducts, respectively. The results of TCNQ are indicative of the gradual formation of two 1:1 equilibrium products. The [A15C5+ TCNQ- ] and 7-A15C5-7,8,8-tricyanoquinodimethane are assigned to these adducts and the rate constant and sum of their formation constants are measured. In the case of bromanil, the conversion to a charge-transfer complex through a nonequilibrium reaction is observed. The rate constant of this reaction was determined. Finally, all of the resulting complexes were isolated in crystalline form and the effect of complex formation on IR spectra is discussed.

Spectrophotometric Study of the Interaction Between Aza-15-Crown-5 and Some p-Acceptors in Chloroform Solution

A spectrophotometric study concerning the interaction between A15C5 as n-donor and TCNE, DDQ, TCNQ and bromanil as p -acceptor was been performed in chloroform at 25 °C. The results of TCNE indicate the formation of a 1:1 charge-transfer complex through a nonequilibrium reaction. In the case of DDQ, the formation of 1:2 (A15C5/DDQ) and 1:1 charge-transfer complexes through equilibrium and nonequilibrium reactions is confirmed. The formation constant of the equilibrium step was evaluated from the computer fitting of the absorbance-mole ratio data as logKf = 5.14 \pm 0.09. The [A15C5+ (DDQ)2- ] and [A15C5+DDQ- ] are suggested as the possible 1:2 and 1:1 adducts, respectively. The results of TCNQ are indicative of the gradual formation of two 1:1 equilibrium products. The [A15C5+ TCNQ- ] and 7-A15C5-7,8,8-tricyanoquinodimethane are assigned to these adducts and the rate constant and sum of their formation constants are measured. In the case of bromanil, the conversion to a charge-transfer complex through a nonequilibrium reaction is observed. The rate constant of this reaction was determined. Finally, all of the resulting complexes were isolated in crystalline form and the effect of complex formation on IR spectra is discussed.

___

  • C.J. Pedersen, J. Am. Chem. Soc. 89, 2945 (1967).
  • D.J. Cram and J.M. Cram, Acc. Chem. Res. 11, 8 (1978).
  • K. Morakum, Acc. Chem. Res. 10, 294 (1977).
  • A. Semnani and M. Shamsipur, J. Chem. Soc., Dalton Trans. 2215 (1996).
  • A. Semnani and M. Shamsipur, Spectrochim Acta 49, 411 (1993).
  • R.M. Izatt, J.S. Bradshaw, K. Pawlak, R.L. Bruening and B.J. Tarbet, Chem. Rev. 92, 1261 (1992).
  • R. Mallini and V. Krishnan, J. Phys. Chem. 84, 551 (1980).
  • R. Mallini and V. Krishnan, Spectrochim. Acta 40A, 323 (1984).
  • Y. Jayathirtha and V. Krishnan, Natl. Acad. Sci. Lett. (India), 1, 365 (1978).
  • J. Zolgharnein and M. Shamsipur, Polish J. Chem. 72, 2486 (1998).
  • S. Sadeghi, N. Alizadeh and M. Shamsipur, J. Incl. Phenomn. 34, 431 (1999).
  • M. Shamsipur, Z. Talebpour and N. Alizadeh, J. Solution Chem. 32, 227 (2003).
  • R.M. Izatt, J.S. Bradshaw, S.A. Nielson, J.J. Lamb, J.S. Christensen and D. Sen, Chem. Rev. 85, 271 (1985).
  • R.M. Izatt, K. Pawlak, J.S. Bradshaw and R.L. Bruening, Chem. Rev. 91, 1721 (1991).
  • H.R. Pouretedal, A. Semnani, B. Nazari and A. Firooz, Asian J. of Chem. 17, 329 (2005).
  • H.R. Pouretedal, A. Semnani, B. Nazari and A. Firooz, Asian J. of Chem. 17, 2159 (2005).
  • A. Semnani, B. Shareghi and M.R. Sovizi, Iranian J. of Chem. & Chem. Eng. 19, 67 (2000).
  • A. Semnani, H.R. Pouretedal and B. Shareghi, Iranian J. of Chem. & Chem. Eng. 23, 1 (2004).
  • A. Semnani, H.R. Pouretedal, B. Nazari and A. Firooz, Iranian J. of Chem. & Chem. Eng. 23, 27 (2004).
  • A. Semnani, H.R. Pouretedal, B. Nazari and A. Firooz, Scientia Iranica 10, 1 (2003).
  • M. Shamsipur and H.R. Pouretedal, J. Chin. Chem. Soc. 51, 1 (2004).
  • A. Semnani and M. Shamsipur, J. Incl. Phenomn. 22, 99 (1995).
  • L.J. Andrews and R.M. Keefer, “Molecular Complexes in Organic Chemistry”, Holden Day, New York (1964).
  • M.T. Beck and I. Nagypal, “Chemistry of Complex Equilibria”, John Wiley & Sons (1990).
  • D.A. Skoog, D.W. West and J. Holler, “Fundamental of Analytical Chemistry”, Saunders College Pub- lishing (1998).
  • J.B. Arteburn, Tetrahedron 57, 9765 (2001).
  • T. Satoh, A. Nakamura and A. Iriuchijm, Tetrahedron, 57, 9689 (2001).
  • G. Bringmann and S. Tasler, Tetrahedron 57, 31 (2001).
  • S. Ma, X.D. Zhang and L.L. Shen, J. of Photochem. Photobiol. 139, 97 (2001).
  • R. Foster, “Organic Charge-Transfer Complexes”, Academic Press, London and New York (1969).
  • G.D. Christian and J.E. O’Reilly, “Instrumental Analysis”, Allyn and Bacon (1986).
  • V.A. Nicely and J.L. Dye, J. Chem. Educ. 48, 443 (1971).
  • W.E. Wentworth, J. Chem. Educ. 42, 162 (1962).
  • M.J.D. Powell, Comput. J. 7, 155 (1964).
  • W.R. Hertler, H.D. Hartzler, D.S. Acker and R.L. Benson, J. Am. Chem. Soc. 84, 3387 (1962).
  • M.C. Grossel and S.C. Weston, J. Phys. Org. Chem. 5, 533 (1992).
  • L.R. Melby, R.J. Harder, W.R. Hertler, R.L. Benson and W.E. Mochel, J. Am. Chem. Soc. 84, 3374 (1962).
  • A.F. Garito and A.J. Heeger, J. Acc. Chem. Res. 7, 232 (1974).
  • R.C. Wheland and J.L. Gillson, J. Am. Chem. Soc. 98, 3916 (1976).
  • N.S. Bhacca and D.H. Williams, Tetrahedron Lett. 3127 (1964).
  • I.N. Levine, “Molecular Spectroscopy”, Wiley-Interscience, (1975).
  • H.A. Benesi and J.H. Hildebrand, J. Am. Chem. Soc. 71, 2703 (1949).
  • A.M. Nour El-Din, Spectrochim. Acta 42A, 631 (1986).
Turkish Journal of Chemistry-Cover
  • ISSN: 1300-0527
  • Yayın Aralığı: Yılda 6 Sayı
  • Yayıncı: TÜBİTAK
Sayıdaki Diğer Makaleler

Manganese(III) Acetate Mediated Free Radical Cyclization of 1,3-Dicarbonyl Compounds with Sterically Hindered Olefins

Mehmet YILMAZ, Emre BİÇER and A. Tarık PEKEL

Reactions of Alkenes with Sodium Perborate and Sodium Chloride

Erdal ŞENOCAK, Yavuz TAŞKESENLİGİL Ferhan TÜMER, Cavit KAZAZ, Ferhan TÜMER

Construction and Characterization of Indium Liquid Ion Selective Electrodes Based on Crown Ethers in a PVC Matrix Membrane

Najwa I. ABDULLA, Abdul-Muhsin Al--HAIDER

Extraction-Spectrophotometric Determination of Trace Amounts of Barium and Strontium by 18-Crown-6 and Rose Bengal Using Partial Least Squares

Jahanbakhsh GHASEMI

Interpretation of Sorption Kinetics for Mixtures of Reactive Dyes on Wool

Elif ŞAHİN

Investigation of Electron Transfer Reaction Between Diphenylbenzidine and Ascorbic Acid

Iftikhar Imam NAQVI, Abida PERVEEN

Heterogeneous Electron Transfer Rate Constants of Viologen at a Platinum Disk Electrode

Naheed Kaukab BHATTI, M. Sadiq SUBHANI, Ather Yaseen KHAN

Characterization of TiO2 Synthesized in Alcohol by a Sol-Gel Process: The Effects of Annealing Temperature and Acid Catalyst

Funda SAYILKAN, Meltem ASİLTÜRK, Hikmet SAYILKAN

Characterization of $TiO_2$ synthesized in alcohol by a sol-gel process: The effects of annealing temperature and acid catalyst

Ertuğrul ARPAÇ, Murat AKARSU, Meltem ASİLTÜRK, Yunus ÖNAL, Hikmet SAYILKAN, Funda SAYILKAN

Catalytic Oxidation Properties and Characterization of LaSrCo0.9B'0.1O4 (B'= Mn, Fe, Ni, Cu) Mixed Oxides

Laitao LUO, Guangxin SHAO, Zhanhui DUAN