International Journal of Chemical Science and Technology (ISSN: 2248-9797) Volume 1-Issue4, October 2011.pp.158-167 www.ijcst.

net

Buttressing Effect and Angle of Twist in Alpha-Aryl Pyridines

P. Tomasik
Chemistry Department, Agricultural University of Cracow, Al. Mickiewicza 21, 31-120 Krakw

K. M. Darwish*
Chemistry Department, Science Faculty, Garyounis University, Benghazi Libya. Corresponding Author E mail: khaliddarwish1962@yahoo.com

ABSTRACT : The ortho effect is studied in pyridine systems in which the lone electron pair of the nitrogen atom is expressed as the reaction site. The process obscured by the ortho effect is the interaction between metal ions and this reaction site in 2-phenyl and 2- p- arylpyridines. The ortho effect is manifested by the twist of phenyl or aryl group out of the plane of the pyridine ring. The angle of twist is calculated from the Braude-Sondheimer equation1 that involves the molal extinctions of the 1La 1A absorption bands in the UVspectra of the compounds studied. Due to the ortho effect in these compounds the intensity of the 1La 1A band is reduced. The angle of twist in these compounds depends on the substituents (hydrogen, nitro, amino and acetylamino groups) residing in the aryl group. These substituents do not exhibit any remarkable buttressing effect.

1. INTRODUCTION The ortho effect in presented arylpyridines is a result of several effects operating simultaneously These mutually dependent effects include (1) Inductive (stronger than that transmitted from the para position) (2) Resonance effect (weaker, due to possible twist of group out of the plane of benzene ring) (3) Interaction through the space (4) Steric hindrance (5) Intramolecular hydrogen bonding (6) Buttressing effect which affects all the previous effects composing the ortho effect. The ortho effect with the involvement of the aza atom as the reaction site may be approached on two manners. The first is dealing with the selection of appropriate reaction series with variable 2X-substituents. In this series the reaction site will be attacked by the same reagent. The second approach deals with studying the effect of variable reagent upon one 2-substituted pyridine derivative. The latter case is our field of study in this paper. This model is suitable for studying an intervention of one of components of overall ortho effect. This component is the so-called buttressing effect. Buttressing effect is due to the resonance interaction between the reaction site (the endocyclic ring nitrogen atom) and the substituent (the aryl group). It either prohibits or favours the steric release by the twist of substituent out of the plane of aromatic ring.
X = NO 2 : e - withdrawing, larger twist for more favorable complex and ion-dipole pair formation X = H : No twist, aromatic rings give planner and conjugated system in cyclohexane X = NH 2, NHAc : e - donating, more resonance coupling between rings, less twist leading to obstructed metal-to-ligand coordination X

..

+ N . metal X
n+

metal

n+

This case forces the lone electron pair orbital of the pyridine ring nitrogen atom to suffer significant steric hindrance and as a result become available for any interacting metal cation only by the possible twist of phenyl group. Buttressing effect was preliminarily investigated via the interaction between various metal cations and the lone electron pair orbital of the aza atom in 2-phenylpyridine. Thus 2-phenylpyridine in cyclohexane solution should possess both rings in the same plane and the electron system of both of them should be conjugated.

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This result formed a standard for further comparisons included in studying similar effect with 2- (p-nitrophenyl)pyridine, 2- (p-acetylaminophenyl)pyridine and 2- (p-aminophenyl)pyridine applied as the ligands in the complexes and ion-dipole pairs supposingly formed. The groups residing in the para-position of the phenyl ring were supposed to form a buttress. Previous studies2 revealed that the resonance interaction between the pyridine nitrogen atom and any electron withdrawing - substituent is reduced to minimum. Since p-nitrophenyl group is an electron withdrawing substituent the order of bond between both aromatic rings should be closer to unity than that in the case of that bond in 2-phenylpyridine. This fact speaks of the easy steric release from 2-p-nitrophenyl group and the formation of stronger complexes or ion-dipole pairs with various metal cations. Following this pathway of deduction, the twist of p-aminophenyl and p-acetylaminophenyl groups should be obstructed by the electron donation from these substituents and in consequence the species formed should be less stable. Consequently, the order of influence on the stability of species should be as follows:

The angle of twist depend on size, charge, polarity and electrophilicity of the approaching metal cation. At the same time the angle of twist can be influenced by any para-substituent of the phenyl group (aryl group). Thus electron withdrawing groups ( for instance NO 2 group) reduce the resonance coupling between both rings, and make the rotation of the aryl group more favorable and in conclusion provide conditions for stronger metal to ligand interaction. On the other hand electron donating groups (for instance NH2 group) increase the resonance coupling between both rings and prohibit the twist of the aryl group and obscure the metal to ligand coordination. The so-called buttressing effect can be overshadowed by the obvious substituent effects. If it so, 2-(p-aminophenyl) pyridine should interact more strongly with metal cations than 2-(p-nitrophenyl) pyridine. The UV spectroscopy seems to be a suitable tool for studying these effects. In this method comparison can be made for the molal extinctions at the maximum of the 1La 1A band in the spectra of 2-(p-X-phenyl)pyridines (X = H, NO2, NH2, NHCOCH3) run in aqueous solutions of some metal salts ( x) and in cyclohexane () and the angle of twist () can be calculated from the Braude - Sondheimer equation1: Based on the identity criterion with the observation in the case of 2-phenylpyridine (taken as a standard without steric effect being planner) the importance of buttressing effect can be deduced. 2. EXPERIMENTAL PART All chemicals (solvents and salts) used were of analytical grade. Water was redistilled and organic ligands were prepared according to the literature methods. 2-(p-Nitrophenyl)pyridine was prepared by decomposition of the p-nitrophenylbenzenediazonium chloride in pyridine according to Haworth et al.16 This free radical reaction gives the three (2-, 3-, and 4-) p-nitrophenylated products. An aqueous solution of p-nitrobenzenediazonium chloride (from p-nitroaniline, 70 g) was added dropwise during 2h to pyridine (500 cm3) stirred at 40 C; the heat of reaction maintained the temperature. Nitrogen was freely evolved. The reaction was completed by warming on the steam bath for 1h. The mixture cantaining some nitrophenylpyridine in suspension was then poured into a large volume of water and the brown precipitate obtained was filtered off, washed, and dried in a steam oven. The product (75 g) was dissolved in boiling benzene (300 cm3) and filtered from some insoluble matter. When cold, a yellow solid (0.5 g) separated, which after sublimation in vacuum and crystallization from nitrobenzene yielded a compound, regarded as , '-di-p-nitrophenylpyridine in fibrous needles of m. p. 293 C. Removal of benzene from the filterate left a yellow solid residue of nitrophenylpyridines (55 g, m. p. 105 115 C). Separation into the constituent isomerides was effected by the method of Forsyth and Pyman; 100 g of the purified mixed nitrophenylpyridines giving - m. p. 130-131C, - m. p. 146-147 C, - m. p. 122-123 C. The crude bases (200 g) were dissolved in hot 5N-

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hydrochloric acid (1.2 L) and solution was digested with charcoal, filtered and kept. The hydrochlorides of 2- and 4-isomerides that crystallized were collected and further crops were obtained by condensation of the mother liquors. The bases regenerated from the crystalline hydrochlorides were crystallized fractionally from alcohol; the 2-isomeride was then obtained in nearly pure state. Its purification was completed by further crystallization from 5N- hydrochloric acid followed by crystallization of the base from alcohol. The fraction of the base most soluble in alcohol gave on crystallization from 5N- hydrochloric acid the hydrochloride of the 4-isomeride. After recrystallization as hydrochloride and then as a base from acetone the 4isomeride was obtained in a pure state. The purity of the final product was controlled by thin layer chromatography. Thus the ethanolic solution of the sample was put on the start of silica-gel precoated aluminium foil (manufactured by merck) and developed subsequently by cyclohexane, benzene, ether, ethanol. After each developing the plate was observed under the UV-light (254 nm). The pure compound left always single non-tailing spot on the plate. 2(p-Aminophenyl)pyridine was prepared by reduction of 2(p-Nitrophenyl)pyridine by two ways: Accoding to Forsyth and Pyman17 : 2(p-Nitrophenyl)pyridine (20 g) was reduced by tin foil (40 g) and concentrated hydrochloric acid (120 cm3). The solution was diluted with water and after removal of tin by conc. NaOH (formation of soluble Na2SnO2), then the 2-(paminophenyl)pyridine separates. It crystallizes from ether (as a free base) or from alcohol. The purity of the compound was checked by the thin layer chromatography as described above. M. p. 97- 98 C. According to Tomasik18 : Reduced iron powder (20 g) was suspended in an aqueous solution (20 mL) of glacial acetic acid (2 mL) followed by portionwise addition of 2(p-Nitrophenyl)pyridine (5 g). After addition of each portion of the nitro-compound the content of the beaker is stirred with glass rod. If the reaction does not appear to be exothermic the reaction vessel is immersed into the steam bath. When the reduction is completed the reaction mixture is left in the steam bath for 30 minutes followed by addition of anhydrous sodium carbonate (10 g) which was thoroughly homogenized with the reaction mixture. The resultant alkalized solid was extracted with hot chloroform. The extract was evaporized to dryness and the left dry residue was crystallized from ethanol. The purity of the product was controlled by thin layer chromatography as above. M. p. 9798C. 2(p-Acetylaminophenyl)pyridine was prepared by heating 2(p-Aminophenyl)pyridine with excess amount of acetic anhydride on a steam bath. After 5 h the reaction mixture was left to stand for 24 h followed by evaporation on the steam bath. The white or yellowish crystals which precipitated were crystallized from hot water. The yield of product was quantitative. M. p. 85 C. 2-Phenylpyridine was prepared according to Forsyth and Pyman17 by decomposition of benzenediazonium chloride in pyridine. Similarly as in the case of 2(p-Nitrophenyl) pyridine three isomers are formed. They were isolated by ethanol and acetone crystallization of their picrates. Picrates were then decomposed by 40 % aqueos NaOH. The liberated 2-phenylpyridine was extracted by ether and after removal of ether the residue was distilled under reduced pressure. The purity of the compound was checked in the usual manner using thin layer chromatography. The UV- spectra were recorded using the double-beam Pye - Unicam 1800 spectrophotometer equipped with 1 X10-3m quartz cells. The solutions of pyridine derivatives in salts were prepared in such a manner that the concentration of salt exceeded that of the ligand by four orders. 3. RESULTS AND DISCUSSION The twist of any substituent results in partial deterioration of the conjugated -electron system and in consequence reduces the delocalization of electrons. This is manifested by lowered propabilities of the 1La 1A electronic transition in the molecule measure of which is the intensity of a relevant spectral band. In this manner always x < if any possible twist of

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Table. 1 UV-spectral characteristics of 2-phenyl pyridine Solventa

Cyclohexane Ethanol H2O HCl (0.1M) LiCl LiNO3 NaCl NaNO3 KCl KNO3 CsCl CsNO3 MgCl2 Mg(NO3)2 CaCl2 Ca(NO3)2 SrCl2 Sr(NO3)2 BaCl2 Ba(NO3)2 Pb(NO3)2 CuCl2 Cu(NO3)2 AgNO3 ZnCl2 Zn(NO3)2 CdCl2 Cd(NO3)2 La(NO3)3 CrCl3 Cr(NO3)3 CoCl2 Co(NO3)2 MnCl2 NiCl2 Ni(NO3)2

(nm)
211, 216, 250 , 270, 298 250*, 268 250*, 270 210, 246*, 294 248*, 268 254*, 272 249*, 270 252*, 270 248*, 274 252*, 270 248*, 270 251*, 270 247*, 272 254*, 270 249*, 271 254*, 270 249*, 270 250*, 270 249*, 271 249*, 270 255*, 288 249*, 273 258*, 275 250*, 251*, 271 254*, 277 210*, 247, 288 255*, 274 255*, 277 253*, 275 255*, 291 250*, 272 255*, 272 249*, 272 254*, 270 255*, 271
*

max*
*

Cos2
0.000 0.993 0.942 0.399 0.862 0.870 0.775 0.746 0.696 0.804 0.877 0.761 0.833 0.841 0.797 0.790 0.797 0.659 0.862 0.594 0.362 0.645 0.725 0.797 0.819 0.616 0.543 0.790 0.674 0.725 0.587 0.819 0.674 0.797 0.862 0.681 00.00 4.88 13.93 50.85 21.78 21.17 28.29 30.24 33.48 26.25 20.55 29.28 24.09 23.53 26.77 27.28 26.77 35.70 21.78 39.57 52.99 36.58 31.65 26.77 25.19 38.29 42.53 27.28 34.82 31.65 39.99 25.19 34.82 26.77 21.78 34.40

13200, 8800,13800 , 8000, 2000 13700*, 11600 13000*, 10000 13000, 5500*, 14900 11900*, 9500 12000*, 12100 10700*, 9700 10300*, 9600 9600*, 8700 11100*, 9700 12100*, 10100 10500*, 9700 11500*, 10700 11600*, 10300 11000*, 9500 10900*, 10600 11000*, 9300 9100*, 6500 11900*, 10300 8200*, 9700 5000*, 12100 8900*, 8700 10000*, 11400 11000* 11300*, 11300 8500*, 11300 12900*, 7500, 12700 10900*, 12300 9300*, 11600 10000*, 12000 8100*, 12500 11300*, 11100 9300*, 9800 11000*, 9500 11900*, 12600 9400*, 13900

the substituent takes place. The set of x values was measured for all four pyridine derivatives, dissolved in aqueous solutions of either nitrates or chlorides of the following metals: Li, Na, K, Cs, Mg, Ca, Sr, Ba, Pb (II) (only nitrate), Cu (II), Ag (I) (only nitrate), Zn, Cd, La (only nitrate), Mn (II) (only chloride), Cr (III), Co (II), and Ni. The concentration of the relevant metal cations was by ~ 4 orders higher (10 -1M) than that of the pyridine derivatives (5 x 10-5 M) to shift of the equilibrium towards complex or ion-dipole pair: Simultaneously, based on the experience of many authors3 the species studied are believed to have anion of the salt beyond the inner coordination sphere of eventual complex. Thus they have the general formula MLn+. Moreover the values introduced into the Braude-Sondheimer equation are taken from cyclohexane spectra of the four pyridine derivatives. Only in solutions with solvent-solute interactions limited to the van der Waals forces and without solvation of the lone electron pair of the aza-atom both rings may be believed to be planner. Comparison of intensities of the 1La 1A band in cyclohexane, aqueous and ethanolic spectra allows to realize that due to hydration and solvation by alcohol the aryl groups are twisted by the angles given in tables 1- 4. In these spectra the most intensive band is the 1La 1A band (actually ICT intramolecular charge transfer band in the case of the nitro derivative, which can be subject to correlation, unlike that in the spectra of 2-phenylpyridine). In the 2-phenylpyridine spectra the most intensive band at 250 nm is the 1La 1A band. It partly hides more longwavelengths band of lower

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Table. 2 UV-spectral characteristics of 2-(p-nitrophenyl) pyridine Solventa

Cyclohexane Ethanol H2O HCl (0.1M) LiCl LiNO3 NaCl NaNO3 KCl KNO3 CsCl CsNO3 MgCl2 Mg(NO3)2 CaCl2 Ca(NO3)2 SrCl2 Sr(NO3)2 BaCl2 Ba(NO3)2 Pb(NO3)2 CuCl2 Cu(NO3)2 AgNO3 ZnCl2 Zn(NO3)2 CdCl2 Cd(NO3)2 La(NO3)3 CrCl3 Cr(NO3)3 CoCl2 Co(NO3)2 MnCl2 NiCl2 Ni(NO3)2

(nm)
300 302* 302* 297* 303* 303* 302* 302* 300* 303* 303* 302* 303* 302* 305* 305* 305* 310* 304* 314* 302* 304* 301* 300* 302* 302* 301* 305* 302* 301* 305* 302* 304* 304* 302* 303*
*

max*

Cos2
0.000 0.903 0.968 0.796 0.817 0.871 0.780 0.700 0.699 0.710 0.753 0.726 0.860 0.828 0.736 0.688 0.763 0.553 0.860 0.538 0.699 0.710 0.645 0.785 0.763 0.645 0.860 0.785 0.796 0.726 0.785 0.849 0.677 0.817 0.882 0.745 00.00 18.12 10.35 26.87 25.31 21.05 28.00 33.20 33.28 32.60 29.82 31.58 21.95 24.51 30.88 33.95 29.10 41.92 21.95 42.84 33.28 32.60 36.56 27.63 29.10 36.56 21.95 27.63 26.87 31.58 27.63 22.83 34.61 25.31 20.12 30.33

18600 16800* 18000* 14800* 15200* 16200* 14500* 13000* 13000* 13200* 14000* 13500* 16000* 15400* 13700* 12800* 14200* 10300* 16000* 10000* 13000* 13200* 12000* 14600* 14200* 12000* 16000* 14600* 14800* 13500* 14600* 15800* 12600* 15200* 16400* 13900*

intensity which is the 1Lb 1A . Since the shape between pyridine derivative and the metal ion, can be divided into four types (see reproduced type (Fig 1) resembles the cyclohexane spectrum,

of spectrum suggests the type of interaction the spectra run in aqueous solutions of salts examples of plots in Figures 1- 4). The first i. e. 1La 1A band.

To this type belong spectra measured in cyclohexane, ethanol, water and aqueous solutions of both salts of Li, Na, K, Cs, Ca, Sr, Ba and Mn. Formation of the spectra of this type should be understood as an evidence for weak interactions between cation and lone electron pair of the aza atom. These interactions are too weak to form any complex but strong enough to cause the twist of the phenyl ring. The atoms causing this type are known as weakly coordinating atoms. The number of their complexes with pyridine ligands is almost negligible. The second type (Fig 2) exhibits two bands of approximately equal intensity. To this type belong spectra for Li (nitrate), Mg, Cu (nitrate) and Zn (chloride). The second group of spectra presents an intermediary case between the first and third type of spectra. The coordination ability of atoms responsible for the second type of spectra is unquestionable.3

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Table. 3 UV-spectral characteristics of 2-(p-aminophenyl) pyridine Solventa

Cyclohexane Ethanol H2O HCl (0.1M) LiCl LiNO3 NaCl NaNO3 KCl KNO3 CsCl CsNO3 MgCl2 Mg(NO3)2 CaCl2 Ca(NO3)2 SrCl2 Sr(NO3)2 BaCl2 Ba(NO3)2 Pb(NO3)2 CuCl2 Cu(NO3)2 AgNO3 ZnCl2 Zn(NO3)2 CdCl2 Cd(NO3)2 La(NO3)3 CrCl3 Cr(NO3)3 CoCl2 Co(NO3)2 MnCl2 NiCl2 Ni(NO3)2
*

(nm)
300 307*, 350 296*, 320 239, 289* 297* 296* 297* 295* 296* 270*, 298 296* 295* 297* 297* 285, 296*, 330 285, 296*, 328 296* 295* 296* 299* 280*, 356 296*, 356 253* 279*, 292 284, 294*, 330 296* 294* 332* 320* 354* 290, 353* 295* 355* 296* 296* 294*
*

max*
23400 20600*, 2000 19400*, 14000 9400, 14000* 16500* 14500* 17000* 13500* 15000* 10300*, 15800 17300* 15900* 17300* 18400* 14000, 17800*, 3000 15000, 15100*, 1000 17400* 10500* 20200* 13600* 6200*, 15600 9000*, 15000 13900* 10200*, 11800 15600, 18000*, 4000 12900* 10800* 16900* 13400* 14800* 9900, 12100* 15200* 15100* 17200* 19800* 13300*

Cos2
0.000 0.880 0.830 0.598 0.705 0.619 0.726 0.577 0.641 0.675 0.739 0.679 0.739 0.786 0.761 0.645 0.743 0.449 0.863 0.581 0.667 0.641 0.594 0.504 0.769 0.551 0.462 0.722 0.573 0.632 0.517 0.735 0.650 0.645 0.846 0.568 00.00 20.23 24.42 39.35 32.88 38.05 31.53 40.58 36.80 34.74 30.70 34.48 30.70 27.53 29.28 36.55 30.42 47.94 21.70 40.32 35.26 36.81 39.58 44.76 28.71 42.07 47.21 31.81 40.82 37.32 44.02 31.00 36.30 36.50 23.09 41.07

The third type (Fig 3) have the 1La 1A band less intensive than the 1Lb 1A band. To this type belong spectra for Cu, Ag, Zn (nitrate), Cd (nitrate), La, Cr (chloride), Co and Ni. This group of spectra suggests much stronger interactions between 2-phenylpyridine and the metal cation. Such atoms like Li and Mg and others accounted to this group are known as those giving weak but isolable solvates. It is well noticed that any transfer from any spectrum of the first type into that of the third is due to the decrease of intensity of the 1La 1A band but also an increase of intensity of the 1Lb 1A band. Therefore one may carefully assume the formation of real coordination bonds between the metal and ligand. The fourth type (Fig 4) resembles that of the 2-phenylpyridinium chloride ( i. e. spectrum of 2- phenylpyridine in 0.1 M HCl). To this type belong those salts which underwent hydrolysis in their aqueous solutions due to protonation by hydrochloric acid. The latter type is particularly pronounced in solutions with more basic 2-(p-aminophenyl)pyridine.

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Table. 4. UV-spectral characteristics of 2-(p-acetylaminophenyl) pyridine Solventa

Cyclohexane Ethanol H2O HCl (0.1M) LiCl LiNO3 NaCl NaNO3 KCl KNO3 CsCl CsNO3 MgCl2 Mg(NO3)2 CaCl2 Ca(NO3)2 SrCl2 Sr(NO3)2 BaCl2 Ba(NO3)2 Pb(NO3)2 CuCl2 Cu(NO3)2 AgNO3 ZnCl2 Zn(NO3)2 CdCl2 Cd(NO3)2 La(NO3)3 CrCl3 Cr(NO3)3 CoCl2 Co(NO3)2 MnCl2 NiCl2

(nm)
212, 218, 274, 296 276, 293* 270, 287* 265, 320* 287* 287* 294* 266*, 285 270, 287* 268*, 285 272*, 288 286* 286* 272* 272*, 287 288* 287* 265*, 322 272*, 288 275*, 290 319* 305* 265, 287* 262, 285* 287* 288* 287* 286* 285* 275, 320* 275, 323* 287* 287* 270, 287* 287*
*

max*
14800, 14800, 15800, 22600 12600, 17500* 12800, 16600* 9000, 14300* 13600* 16600* 15000* 13500*, 14000 12500, 15300* 10500*, 15400 12100*, 15500 14600* 14800* 11000* 13200*, 13400 16000* 15400* 7500*, 13000 12200*, 15000 12000*, 14800 9600* 11000* 4000, 6700* 16500, 16400* 13600* 11400* 14800* 13700* 13200* 6000, 12200* 1100, 12700* 14800* 14300* 12900, 16300* 14800*
*

Cos2
0.000 0.774 0.735 0.633 0.600 0.734 0.663 0.597 0.667 0.681 0.686 0.646 0.655 0.486 0.593 0.708 0.681 0.575 0.664 0.531 0.425 0.486 0.296 0.726 0.602 0.504 0.654 0.606 0.584 0.540 0.562 0.721 0.655 0.632 0.655 00.00 28.36 31.01 37.30 39.13 31.01 35.48 39.39 34.63 34.36 34.09 36.57 35.98 33.76 39.64 32.71 34.36 40.67 35.44 43.22 49.32 45.76 57.01 31.59 39.13 44.74 35.97 38.88 40.16 42.72 41.44 31.87 35.98 37.30 35.98

a : The salt should be understood as its 10 -1M aqueous solution. * : max (at its relevant ) chosen for calculation of Cos2 from the relation max / cyclohexane

Ni(NO3)2

287*

13600*

0.601

39.12

In addition, the type of anion (chloride or nitrate) influences the phenomenon studied. For instance the spectra of 2-phenylpyridine in solution of the chlorides and nitrates of the same metal differ from one another in the intensity of spectral bands and sometimes even in the type of spectra as simply discussed above. There seems to be no regularity of the influence of anion on the observation. According to Pearson theory of hard and soft acids and bases, 4, 5 pyridine is a borderline base. The presence of 2-phenyl group which is weakly electron withdrawing group eventually locate this ligand closer to the hard bases but still in the area of borderline bases. Hence, such base is able to form complexes or at least interact with Lewis acids from all these soft, hard and borderline areas. According to the same theory all H+, Li+, Na+, K+, Mg2+, Ca2+, Sr2+, Mn2+, La3+ and Cr3+ are hard acids, Ag+, and Cd2+ are soft acids, whereas Co2+, Ni2+, Cu2+, Zn2+ and Pb2+ are borderline acids. On the other hand, there is even no qualitative correlation between type of spectra and softness or hardness of cations.

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International Journal of Chemical Science and Technology (ISSN: 2248-9797) Volume 1-Issue4, October 2011.pp.158-167 www.ijcst.net Fig: 1 UV Spectra of 2-phenylpyridine in aq.soln. of SrCl2 Fig: 2 UV Spectra of 2-phenylpyridine in aq.soln. of ZnCl2

Fig: 3 UV Spectra of 2-phenylpyridine in aq.soln. of COCl2

Fig: 4 UV Spectra of 2-phenylpyridine in aq.soln. of CdCl2

Fig 5: Identity Criterion For the Angles of Twist in the Case of Chlorides

Fig 6: Identity Criterion For the Angles of Twist in the Case of Nitrates

These visually prepared results in Fig 5 and Fig 6 differ to a certain extent from those statistically computed (Tab 5).

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Table. 5 The Identity Criterion (Y = aX + b) for interaction of cations with 2-arylpyridines* Series
2-(p-nitrophenyl) 2-(p-aminophenyl) 2-(p-acetylaminophenyl)
*

Anion
NO3 Cl NO3 Cl NO3 Cl

45.76 43.59 48.87 45.79 46.23 47.75

a
1.026 0.952 1.145 1.028 1.044 1.101

b
1.182 1.341 1.733 3.697 4.964 7.361

s
3.289 2.861 3.280 3.977 3.191 4.883

r
0.951 0.956 0.961 0.911 0.956 0.887

Interactions with 2-phenylpyridine are taken as a standard

Table. 6 Correlation of the Effect of Anion upon the Angle of Twist in (Chlorides: Nitrates) Spectral Series
2-(p-nitrophenyl)pyridine 2-(p-aminophenyl)pyridine 2-(p-acetylaminophenyl)pyridine 2-phenylpyridine

Slope of Correlation
0.928 0.898 1.156 1.077

The diagrams (in fig 5 and fig 6) present the criteria of identity for the series of chlorides and nitrates respectively. They are constructed in such a way that all straight lines leave the origin (0.00). According to these diagrams, the slopes in both cases are as follows:
( ( ) ) ( ) ) ( ( ) )

instead of the preliminary assumed All slopes apart from one are above unity ( = 45). In majority of cases the differences are almost within the experimental error. In the spectral series composed of 14 and more experimental points the correlation coefficient > 0.900 can be acceptable.6 In other cases a strong tendency to the linearity is noticed. Imperfect correlations may be due to double cation pyridine base interactions, i. e. in which the aza atom and substituent on the phenyl ring are involved. The electronic effect of the p-substituents in the pyridine moiety upon the basicity and nucleophilicity (softness) of the ligand is important. Based on the electronic properties of these substituents expressed by p-constant of Hammett7 these properties should increase in the following order of p-substituents:
( ) ( ) ( ) ( )

It means that the stability of any metal complex with above ligands should increase in this order. Indeed the UV spectral investigation carried out thoroughly did not show any complex formed between 2-(p-nitrophenyl)pyridine and any of the metal cations used. On the other hand, literature reported the following metal complexes with 2-phenylpyridine (denoted by L):
LAlBr3,8 LTeCl4,9 LCu2+, 10,11 L2CuCl2,12 LZn2+,10LUO2 acetylacetone,13LNi2+,10 L2NiCl2.2H2O, 12 L4NiCl2.2H2O,12 LRhCl(CO)2, 14and L2PdCl2.15

Investigations carried out in our present studies revealed that 2-(p-aminophenyl)pyridine is also capable of forming metal complexes. Isospestic points could be observed as the metal to ligand ratio was changed. Such points could be observed in case of 2-(p-aminophenyl)pyridine with CoCl2 and with CuCl2 and in the case of 2-(p-acetylaminophenyl)pyridine with CuCl2 metal salts. Stability constants could not be calculated as the temperature of measurements was not precisely stabilized. The differences in the case of straight lines in the series of metal chlorides may eventually speak for the intervention of a buttressing effect ( lower twist of p-aminophenyl group than of p-acetylaminophenyl group). The observation of that effect in

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the case of nitrates is perhaps obscured by the effect of the nitrate anion. It can play a role of additional ligand which by its bidentate character more readily than chloride undergoes coordination into either inner or at least outer coordination sphere. The effect of anion can easily be evaluated by similar identity criterion as above using data from table 5. The data in table 6 present slopes of correlations of effects of anions upon the angle of twist within the same spectral series, i. e. containing the same ligand. 4. CONCLUSIONS: 2-Phenyl- and 2-arylpyridines interact with metal cations in aqueous solutions to form either complexes, ion-dipole pairs or pyridinium salts depending on the salt. In the case of unsubstituted 2-phenylpyridines the following type of species could be recognized based on the shape of the UV spectra in aqueous solutions of the salts. Ion-dipole pairs are formed between 2-phenylpyridine and all LiCl, NaCl, NaNO3, KCl, KNO3, CsCl, MgCl2, CaCl2, SrCl2, Sr(NO3)2, BaCl2, Ba(NO3)2, MnCl2, and ZnCl2. Complexes are formed between 2-phenylpyridine and all LiNO3, Ca(NO3)2, Cu(NO3)2, CuCl2, AgNO3, Zn(NO3)2, Cd(NO3)2, La(NO3)3, CrCl3, CoCl2, Co(NO3)2, NiCl2, and Ni(NO3)2. Pyridinium salts are formed in aqueous solutions of all CdCl 2, Pb(NO3)2, Cr(NO3)3, due to the hydrolysis of these salts. The interactions are manifested by the twist of the phenyl (aryl) group and this twist depends on the electronic effect of the group which resides in the aryl moiety. The electronic effect of substituent on the basicity (nucleophilicity) of the pyridine moiety seems to be a major factor governing observed interactions. It can be stated that buttressing effect in the compounds under study operates as a factor of minor importance in comparison with the effects listed under p. 1. The interactions observed are also influenced by intervention coming from anion. The nitrate anion may enter the inner coordination sphere as a bidentate ligand. Authors Statement Competing Interests The authors declare no conflict of interest. 5. REFERENCES:
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