MICROCHESMICAL JOURNAL, 2, 263-267 (1995) Charge-Transfer Complexes of Oxazolones with “Nitrobenzene” 7-Acceptors E. H. EL-Mossatamy axp A. S, AMIN Chemistry Department, Faculty of Science, Benha University, Bewha, Egypt Received June 30, 1994: accepted September 28, 1994 Charge-transfer molecular complexes of some 2-aryl-4-arylidene-5(4) oxazolanes with di- and \rinitrobenzene have been studied at 25°C. The stoichiometry and apparent formation constants ofthe ‘complexes formed were determined by applying the conventional continuous variation method. The role of the molecular structure of the electron donor and acceptor compounds as well as the nature Of the solvent on the formation of such charge-transfer complexes. Furthermore, association con- stants, oseillator sieength, dipole moment, and free energy are elucidated, © 195 Acakemic Pres ln INTRODUCTION ‘The = donor properties of indene are established from its ability to form complexes with hexacarbonyl chromium (/, 2), 1,3,5-trinitrobenzene (3), and 2,4,7-trinitrofluorenone (4). Ithas been reported that in the Schiff bases of aminopyridene (5) and indolylidene formed charge-transfer (CT) complexes with di- and trinitrobenzene. The present article deals with a study on the intermolecular charge-transfer complexes of some oxazolones with di- and trinitrobenzene. Elucidation of the role of molecular structure of the complexes as well as the nature of the organic solvents, the stoichiometry, apparent formation constant, the association constants, and some physical parameters of CT complexes are reported here. EXPERIMENTAL 2-Aryl-4-arylidene-5 (4) oxazolone derivatives were prepared according to the litera- ture (7) as the donors and have the following general formula. x ‘© cx=e—c-0 | N oO Ne74 r #0) 0-0H (b) Picric acid (/), 3.5-dinitrobenzoic acid (II), 2.4-dinitrophenol (Ill), p-nitrophenol (IV), and m-dinitrobenzene (V), were pure grade BDH products. Methylene chloride, benzene, diethylether, carbon tetrachloride, cyclohexane, chloroform, and methyl acetate were pu- x= p-OH (a), 263 (0026-265K/95 $12.00 Spyig © 198 by Asani Pre, Allegis feet nan fem ever264 EL-MOSSALAMY AND AMIN rified according to Vogel (8) and Organicum (9), dried, and distilled. Stock solutions (2 x 10°* M) of cach of the electron donor and acceptor compounds were prepared by dissolving accurately weighed amounts of each compound in the organic solvent. All absorption spectra measurements were made with a Perkin Elmer Model A 3B spectrom- eter RESULTS AND DISCUSSION The association constant of formation (x) and molar extinction coefficient (e) of the CT complexes studied have been determined by utilizing the rearranged form (10) of the Bensi-Hildebrand equation (//), [A] + [D] = €L [AILDVd — Vier. Where [A] and [D} are initial molar concentration of the acceptor and the donor, respectively, L the path length in centimeters, and d the absorption. This equation enables one to determine (K) and (¢) independently for the complexes under the condition of constant [A] and [D] > [A]. The values of € and K are determined from the gradient and negative intercept of the linear plot of [A] + [D] against [A][DI/d (Fig. 1), in which both K and e were evaluated, have been observed also between the molar extinction coefficients (©) and association constants (K) of the CT complexes. The results show a deviation from Mulliken’s theory (2) which predicts that the molar extinction coefficient increases as the (al 1 ia) +10) Fi ‘of oxazolone derivatives wit 1. Spectral determination of equilibrium constants and molar extinction coefficients for CT complexes robenzene (methylene chloride used as solvent at 25°C),TT DONOR PROPERTIES OF INDENE 265 ‘strength of interaction between a donor and an acceptor increases. It has been concluded that (K) values correlate well with both the +-basicity of donor as well as the electron affinity of acceptor but not with (€p,,) (Table 1). From the above calculation, K values were used to compute free energy ~AG* values according (/3): AG* = -RTIn Key The complexes have ~AG* ranging from (0.2-0.7) kcal mol"', indicating the very weak nature of the complexes and spontaneous reaction between D* and A”, but the general trend shows that ~AG* values increase as electron affinity of the acceptor increases or the ionization potential of the donor decreases. It has been reported that the ionization potentials of the electron donors may be cor- related with the transition energy of the complexes of those donors with electron acceptors (14, 15). Table | includes the ionization potential of the donors 2-(0-hydroxyphenyl)-4- (p-hydroxy-benzylidene)-5-(4) oxazolone (a) and 2-(o-hydroxyphenyl)-4-(o-hydroxy ben- zylidene)-5-(4) oxazolone (b) calculated from the frequency values (vey) of their com- plexes with the 7r-acceptors using the following ip (eV) =a + byey Where the coefficients a and b depend only on the electron acceptor and their values are reported by Aloisi (/6) and Mourad (/7). In the application of Job's method (18) for determination the stoichiometry of the CT complexes studied, symmetrical curves were obtained (Fig. 2) which give maxima at a mole fraction equal to 0.5. Thus the stoichi- ometry was assumed to be 1:1, Further support for one-to-one complexes has been observed in the linear plot of the Bensi-Hildebrand equation (Fig. 1). The results of the continuous variation method were applied for the determination of apparent formation constant (K;) of the different 1:1 complexes studies; the following equation, TABLE | The Association Constant (K), Molar Extinction Coefficient (e), Oscillator Strength (f), Transition Energy (2), Free Energy (AG*), Dipolemoment (1. Aya and ip (eV) of the Charge~Transfer Complexes between COxazolone and Nitrobenzene in Methylene Chloride at 25°C Kk E ip -ace Acceptor: Donors )—tmodtier') eV) fecal mol Pie acid a 066 303309049 SAL 0877 “ b 06k «2701 O78 ORK Set OBS 35Dimitro- a 0s? 28270804642 0827 benzoic b 060 ©2764 aS 04246 0583 acid (lly 244 init a 4s 2 oss 278212 as, ost phenol (il) bas a O58 2675128, 04282582 pNiophenol =a 470 36 O40 2646 0m? OF 72 0.653 avy bs 0 Ost 2618058 02K 7380600 Dini a 480 4s O92 2591028023 RAD O74K benzene V) ba 45 0% = 2538026032 SAD TT266 EL-MOSSALAMY AND AMIN i é we Mole faction of the Fie. 2. Continuous variation method for compleses of oxacolome derivative with: (1) foxarolone ts) ~ 1 = 2.8% 10M, Agus = 410 nm: (2) foxazolone (b) ~ = 2.8 x 10M, Agay = 460m: (3) loxazolone (a) — UI] —3 107 AF gg = 440 nem: (4) foxazolone tb) = HH] = 386 10M, gg = 450 nm a AIA, T= Alay where A,, is the limiting absorbance corresponding to the maximum formation of the complex and A the absorbance at electron donor concentration C, was applied (/9, 20). ‘The K;, values abtained are listed in Table 2. On examination of the results given in this table, it is evident that the order of increasing stability of the 1:1 intermolecular charge- transfer complex formed varied depending on the nature of the electron donor and ac- ceptor compound according, respectively, to the following sequence: Picric acid > 3,5- dinitrobenzoic acid > 2,4-dinitrophenol > p-nitrophenal > m-dinitrobenzene. TABLE 2 Effect of Solvents on Band Wavelength Position of the Oxazolone a]-3,5-Dinitrobenzoic Acid (1) Complex (at 25°C) i, on K, E ip Dielectric Solvents (om) mot Pen") (mol fe) (eV) constant (D°C) Ethanol 495 28 04 2513 68 26 Methylene chloride 440. 2% 037 2827-042 89 Benzene 482 os 2580025 22 Chloroform 452 i 032 3759234 48 14-Dioxan 42 rn oss 2947 32 43 Diethyl ether 410. Is oa 303318 22 Methyl acetate 405 6 050 3071 . 68 ccl, 460 B 04s 27044 22 Cyclohexane 450 lo 038 2.764 2011 DONOR PROPERTIES OF INDENE 267 SOLVENT EFFECT The changes in the spectra of oxazolone (a)-3,5-dinitrobenzoic acid complex measured in organic solvents of different dielectric constants were determined and the results are recorded in Table 2. The results show a relatively high shift of the position of the charge-transfer band from 410 nm in ether to 460 nm in carbon tetrachloride. This reflects the high sensitivity of the charge-transfer complex to the polarity of the organic solvents used. The charge-transfer complex measured in nonoxygenated solvent (e.g., benzene, carbon tetrachloride, and cyclohexane) shows that the transition energies decrease as the polarity of the solvent increases. Kosower (2/) reported a similar relationship between the transition energies and the polarity of the solvent. This may be due to the fact that the charge may be more separated in the excited state than in the ground state. The integrated intensity of the absorption bands in methylene chlolide termed the oscillator strength (f) and the transition dipole moment (.) of the CT complexes under examination reported in Table 1 were computed from the following approximate equation (13, 14), P= A432 10-9 Emax “yy H= 0.0958] Eas * Yy2/maxl Where €q,a iS the molar extinction coefficient of absorbance at the CT maximum, tna. the frequency of the CT maximum in cm”', and v4,, is the half width in cm”! It has been reported that as the resonance interaction increases, fand 4 should increase (22). Consequently. the values of f and y decrease according to the order of their ar- rangement in Table {. This irregularity of values perhaps stems from the structural difference of the electron donors (a,b). REFERENCES Fischer, E. 0. Kriebitaseh, N, Z Naturforsch, 1960, 18, 465, Vebret, J. Mereier. R.: Belleny, 3. . Organomet. Chemm.. 1982, 238, 197, Deb, K. K.: Cole, T.C. John, E. Org. Magn. Reson, 1970: 2, 491 I 3 4, Cooper, A. R.: Crowne, C, W, P.. Farrell, PG. Trans, Faraday Soc.. 1967, 63, 447, 5 6 Gaber, M., El-morsi, M. As Ebighfor, M.A. J. Pakistan Chiem, Soc.. 1988, 10, 1 Dessouki, H. A.: Gaber, M. Issa, R, M.: Hossani, EJ. Indian Chem. Soc., 188, 38, 258, 7. Eelenmeyer: Matter. A. 1908, 337, 271 8 Vogel, AL. Text Book of Practical Organic Chemistry, 3rd 08, Longmans, London, 1956. 4, Organicum, Practical Handbook of Organic Chemistry, It ed, Pergamon, Elmsford, NY, 1923, 10, Seal. B. K.: Sil. Hz Mukherjee. D. C. Spectrochim, Acta, 1982. 388, 289, 11, Bonsi, HA. Hildebrand, J. 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