Transition Metal Chemistry (2006) 31:4655 DOI 10.

1007/s11243-005-6312-4

Springer 2006

Binuclear copper(II), nickel(II) and cobalt(II) complexes with N2O2 chromophores of glycylglycine Schi-bases of acetylacetone, benzoylacetone and thenoyltriuoroacetone
Shehab A. Sallam Chemistry Department, Faculty of Science, Suez Canal University, Ismailia, Egypt
Received 9 June 2005; accepted 10 August 2005

Abstract Binuclear copper, nickel and cobalt complexes of the Schi-bases obtained by condensation of glycylglycine with acetylacetone, benzoylacetone, dibenzoylmethane and thenoyltriuoroacetone were prepared by template synthesis. The complexes were characterized by elemental analysis, conductivity measurements, magnetic moments, i.r., u.v.vis. spectra, e.s.r., X-ray diraction, t.g.a., d.t.a. and d.s.c. thermal analysis. All the complexes are nonelectrolytes with low magnetic moments that indicate spinspin or antiferromagnetic exchange interactions. Spectral properties support square planar and square pyramidal or trigonal bipyramidal structure provided by the N2O2 chromophores. E.s.r. spectra of the copper complex conrm the binuclear structure and the presence of magnetic interaction. Thermal studies supported the chemical formulation of these complexes and showed that they decompose in three to four steps depending on the type of ligand. Activation energies Ea and enthalpies DH, associated with the thermal decomposition of the complexes were calculated and correlated with the type of complexed metal. A mechanism for thermal decomposition is proposed for the complexes.

Introduction Systems in which the Schiff-bases of amino acids are derived from b-diketones have received scant interest [13]. Neglect of this ligand type of b-ketoimine-N-alkanoic acid seems to arise from their known hydrolytic instability [4]. Furthermore, those metal complexes primarily have been conned to transition elements. N-benzoylacetoneglycine has been stabilized in the form of its sodium salt and the complexes of this ligand with a series of lanthanide(III) ions have been prepared and their antioxidative actions also have been determined [5]. However, little attention has been paid to systems in which the Schiff-bases are derived from simple peptides. A vanadium complex VO(salglygly)(H2O)n (salglygly = N-salicylideneglycylglycine); n = 1.53.0 has been isolated from relatively concentrated solutions containing oxovandium(IV), glycylglycine and salicylaldehyde [6]. Synthesis, crystal structure and magnetic studies of cis-conguration copper(II)-M(II) (M = Ba, Ca) complexes of the salglygly Schi-base were determined [7]. We have prepared and characterized the uranyl complexes of Schi-bases obtained by condensing glygly with hydroxybenzaldehydes and hydroxynaphthaldehyde [8]. Recently, two copper(II) tripeptide Schi-base complexes: [Mg(H2O)6] [CuL]2 3.5H2O and [Cd(H2O)4(CuL)2] 3 . 5H2O (H3L =
E-mail: [email protected]

N-salglygly) have been synthesized and structurally characterized [9]. Also, reaction of Na[CuL] (where H3L = the Schi-base derived from 5-bromosalicylaldehyde and glylgly) with La(NO3)3 leads to the formation of carboxylate-bridged polynuclear copper(II)lanthanide(III) rings of formula [Ln(H2O)5 (CuL)2][CuL] 8H2O (Ln = La and Ce) [10]. In continuation of our interest in the coordination behavior of Schiff-bases of the biologically important glycylglycine, we report the synthesis and characterization of a series of copper(II), nickel(II) and cobalt(II) complexes of Schiff-bases obtained by condensing glycylglycine (glygly) with acetylacetone (acac), benzoylacetone (ba), dibenzoylmethane (dbm) and thenoyltriuoroacetone (tta). The following Schiff-bases were synthesized in solution: L1(glygly + acac), L2(glygly + ba), L3(glygly + dbm) and L4(glygly + tta). The complexes were characterized using: elemental analysis; conductivity measurements, magnetic moment determinations; X-ray diraction; e.s.r., u.v.vis., i.r., and thermal analysis (t.g., d.t.g., d.t.a. and d.s.c.).

Experimental Materials Glycylglycine was obtained from BDH. Acetyl acetone, benzoylacetone, dibenzoylmethane and then-

47 oyltriuoroacetone were purchased from Fluka and were used as supplied. Other chemicals are reagent grade and were used without further purication. Template synthesis of the complexes To a solution of glycylglycine (0.324 g, 2 mmol) and sodium acetate (0.328 g, 4 mmol) in H2O (10 cm3), a solution of the b-diketone (1 mmol) in absolute EtOH (5 cm3) was added dropwise with stirring. The reaction mixture was heated with stirring on a water bath for 2 h during which time the color changed to yellow, indicating formation of the corresponding Schi-bases. The respective metal chloride (2 mmol) in absolute EtOH (5 cm3) was added dropwise to the reaction mixture. The whole mixture was boiled with stirring for 30 min. The precipitated complexes were then ltered, washed several times with EtOH and Et2O, and dried in vacuum over anhydrous CaCl2. Physical measurements C, H, and N were estimated using a Heraus CHNrapid analyzer. Metal analyses were carried out on an ARL 3410 ICP sequential spectrophotometer at wavelengths 324.75, 231.60 and 228.62 nm for Cu, Ni and Co, respectively. The i.r. spectra were recorded (KBr disc) in the 4000400 cm)1 range on Nicolet Impact 400 and Bruker Vector 22 spectrophotometers. The electronic absorption spectra were obtained using nujol of mull and 10)3 M DMSO solutions in a 1 cm cell using a PerkinElmer S550 spectrophotometer. Solid state x-band e.s.r. spectra were recorded on a Varian E4 spectrophotometer. Magnetic susceptibility measurements were carried out using the modied Gouy method on a JohnsonMatthey balance at room temperature and using mercury(II) tetrathiocyanatocobaltate(II) as the calibrant. The eective magnetic moments, le, per metal atom was calculated from the expression:
p "eff 2:83 1:T B.M.

complexes. X-ray powder diffraction was performed using a Shimadzu XD-3 diffractometer with Cu-Ka radiation. T.g.a., d.t.g., d.t.a. and d.s.c. were recorded on a PerkinElmer 7 Series thermal analyzer equipped with Pyres software under a dynamic ow of nitrogen (10 L/min.) and heating rate of 10C/min from ambient temperature to 1000C (t.g.a and d.t.a.) or to 600C (d.s.c.). The number of decomposition steps was identied using d.t.g. Electrical conductivity measurements were carried out at room temperature on freshly prepared 10)3 M DMSO solutions using a WTW conductivity meter tted with a L100 conductivity cell.

Results and discussion All the metal complexes are insoluble in common organic solvents such as methanol, ethanol, benzene, chloroform, acetone, dichloroethane and diethyl ether, but partly soluble in DMSO. The analytical data (Table 1) show that the complexes can be represented as [M2 L1] 2H2O where M = CuII, NiII and CoII and [M2 L24 Cl2 (H2O)2] nH2O where M = NiII and CoII. The low molar conductance values of 10)3 M solutions of the complexes in DMSO at room temperature lie in the 1755 lS range which show that they are all non-electrolytes [11] and that the anion is also coordinated to the metal ion. Infra-red spectra Free glycylglycine has a strong absorption band at 3300 cm)1, which corresponds to the NH2 stretching frequency [12]. In addition, a weak band near 3080 cm)1 was noted and assigned tentatively to an additional NH absorption [12]. Uncoordinated acetylacetone contains the free carbonyl entity that has an intense absorption band at ca. 1700 cm)1 [13]. All these bands are not observed in the spectra of the complexes [Cu2 L1] 2H2O, [Ni2 L1] 2H2O, and [Co2 L1] 2H2O (Table 2). Besides, the strong bands around 1530 and 1280 cm)1, which are characteristic of stretching and bending modes of the bonded

where v is the molar susceptibility corrected using Pascals constant for the diamagnetism of all atoms in the

Table 1. Analytical data, electrical conductivities and magnetic moments of the synthesized complexes Complex [Cu2 L1] 2H2O Ni2 L1 2H2 O [Co2 L1] 2H2O [Ni2 L2 Cl2 (H2O)2] H2O [Co2 L2 Cl2 (H2O)2] 2 H2O [Ni2 L3 Cl2 (H2O)2] 3H2O [Co2 L3 Cl2 (H2O)2] 3H2O [Co2 L4 Cl2 (H2O)2] 2 1/2 H2O chr=charring. Color Mol. wt. M.p. (C) 246 345 295 207 300 chr 360 >400 307 chr Found (calcd.)% C N 32.4(32.0) 32.5(32.7) 32.8(32.7) 32.9(32.6) 31.6 (31.5) 37.3(37.2) 37.2 (37.2) 23.8(23.9) 11.1(11.5) 11.1(11.7) 11.3(11.7) 5.5(5.4) 5.4 (5.2) 4.7(4.6) 4.7 (4.6) 4.3(4.6) X (lS) H 3.8(4.1) 4.0(4.2) 3.8(4.2) 3.43(3.7) 3.6(3.55) 4.0(4.1) 3.85(4.1) 3.01(2.8) M 26.0(26.1) 25.3 (24.6) 25.1(24.7) 22.65(22.8) 22.2 (22.1) 19.3(19.3) 19.34(19.2) 19.8 (19.55) 17 28 47 33 45 31 43 55 0.31 Dia. 1.25 0.6 0.74 0.80 0.64 1.13 le B.M.

Green Olive Pink Olive Pink Olive Pink Pink

487.13 477.43 477.91 515.35 533.82 613.38 613.86 602.82

48
Table 2. Spectral data of the complexes
Complex I.r. spectral data. (cm)1) mOH mNH mC=N masCOO) mCO msymCOO) mCN dCOO) MO MN 411 m 484 m 420 m 484 m 443 525 428 452 435 464 417 467 417 462 412 467 m m m m m m m m m m m m Vis. spectral data (cm)1) Nujol DMF

[Cu2 L1] 2 H2O

3400 s. sh

3232 s. sh 3082 s. sh 3361 s. m 3273 s. sh 3366 s. sh 3287 s. sh 3064 m 3366 s. sh 3268 m. br 3366 s. sh 3281 m. sh 33656 m. b 3268 m. br 3363 m. br 3279 m. br

1637 s

1587 s

1515 m

1429 ssh

1403 m

760 m

Ni2 L1 2H2 O

3430 m. sh

1637 s

1587 s

1429 ssh

1405m

760 m

[Co2 L1] 2H2O [Ni2 L2 Cl2 (H2O)2] H2O [Co2 L2 Cl2 H2O] 2H2O [Ni2 L3 Cl2 (H2O)2] 3H2O [Co2 L3 Cl2 (H2O)2] 3H2O [Co2 L4 Cl2 (H2O)2] 2 1/2H2O

3451 s. sh 3451 m. br 3451 m. br 3454 m. sh 3458 m. br 3462 m. br

1641 s 1600 s 1646 s 1646 s 1640 s 1646 s

1585 s 1564 s 1575 s 1575 s 1582 s 1578 s

1518 s 1552 s 1567 s 1555 s 1552 s

1444 m sh 1454 m sh 1444 m sh 1444 m sh 1441 m sh 1444 m sh

1403 m 1398 br 1400 m 1406 m 1405 m 1400 m

755 m 763 m 759 m 759 m 760 m 759 m

14,204 sh 18,135 22,988 14,925 17,699 25,641 18,281 br 13,020 sh 15,748 br 18,050 br 13,254 sh 15,037 br 17,960 br 17,985 br

14,306 br 11,152 sh 13,458 14,749 23,923 15,128 16,051 sh 13,254 sh 15,220 br 19,607 13,054 14,641 19,540 19,230

carbonyl of acetylacetone, are absent [13]. The above i.r. data clearly indicate that, in these complexes, the carbonyl groups of one molecule of acetylacetone have reacted with the amine groups of two molecules of glycylglycine through the template eect of the metal atoms. This contention is supported by the presence of new bands in the spectra of the complexes in the 29272965, 13211330, 12671275, 11031130 and 609615 cm)1 ranges which are characteristic of the acetylacetone moiety and may be assigned to )CH3, dsCH3, )CCH3, dCH + )CCH3 and to ring deformation, respectively [1315]. Also, new bands characteristic of the )(NCO) appear in the 15151549 and 13211327 ranges due to coordination through imidol oxygen [16]. I.r. spectra of the complexes [Ni2 L2 Cl2] H2O, [Co2 L2 Cl2] 2H2O, [Ni2 L3 Cl2] 3H2O, [Co2 L3 Cl2] 3H2O and [Co2 L4 Cl2 (H2O)2] 2 1/2H2O show the disappearance of )(C O) of the b-diketone part and the appearance of new bands in the 15181567 cm)1 range assignable to )(CO) which suggest that the carbonyl group is involved in coordination in the enol form through deprotonation [17]. The i.r. spectra of all the complexes show broad bands in the 33323368 cm)1 range that may be well correspond to )NH amide. Also, a sharp strong band in the 16371646 cm)1 range indicates the presence of bonded azomethine groups (>C N) [17]. The strong broad bands, present in the 15751587 cm)1 range in the complexes spectra, are assigned to an asymmetric stretch of coordinated carboxylate groups. Bands corresponding to )sym(COO)) appear in the 14291444 cm)1 range, giving a frequency dierence (D) value) of 131158 cm)1 compared with 171 cm)1 of free glygly that reect the monodentate nature of the carboxylate groups [18, 19]. Strong absorption

bands in the 13981405 cm)1 range could be assigned to the CN amide stretching mode [16]. The carboxyl wagging vibrations appear in the 755760 cm)1 range in the complexes spectra. Bands in the 411420 cm)1 range in the complexes spectra are assigned to the MO stretch. The )(MN) vibration is attributed to the bands in the 443525 cm)1 range [13]. Magnetic and spectral properties The magnetic moments of the complexes calculated from the corrected magnetic susceptibility determined at room temperature are given in Table 1. The magnetic moments reported for the complexes are lower than the spin only values. The subnormal magnetic moments observed for the Cu, Ni, and Co complexes are accounted for by assuming a binuclear structure with considerable interaction between metal ion systems owing to spinspin coupling causing an antiferromagnetic interaction mechanism to operate through the orbitals of the metal ions [2022]. The magnetic moment per copper atom in the [Cu2 L1] 2H2O complex is below the spin only value of 1.73 B.M. for copper(II). Such lowering of the magnetic moment has been observed in the bi- and trinuclear complexes, which contained only copper(II) and has been shown to arise from antiferromagnetic exchange interactions [20, 2325]. The observed magnetic moment indicates fairly strong magnetic exchange interaction between pairs of neighboring copper atoms, a phenomenon which occurs in a large number of copper(II) complexes [20]. The copper complex possesses square planar geometry as evidenced by the appearance of only one band in the electronic spectra (nujol mull) at 14306 cm)1 with two shoulders at 18135 and 22988 cm)1. These

49 bands could be assigned to 2B1g 2A1g, 2B1g 2B2g and 2B1g 2Eg transitions, respectively [26]. The square planar coordination of each copper atom is provided by the two N2O2 chromophores of the Schibase. One of the copper atoms forms a six-membered ring and two ve-membered rings. The second copper atom forms two ve-membered rings. This geometry may probably lead to a greater antiferromagnetic interaction [27]. Upon dissolution in DMSO, the complex changes from green to violet and the spectra of the solution show a broad band at 14306 cm)1 with a shoulder at 11152 cm)1. This indicates that, in solution, the copper complex changes geometry from square planar to distorted octahedral with 2Eg 2T2g and 2B1g 2A1g transitions through the adduction of solvent molecules [28]. The complex [Ni2 L1] 2H2O displays diamagnetic behavior. This is consistent with square-planar geometry of the two N2O2 chromophores around the Ni(II). This interpretation is supported by electronic spectra in the nujol mull (Table 2). It shows three absorption bands at 14925, 17699 and 25641 cm)1 which are attributed to 1A1g 1A2g()1), 1A1g 1B1g()2) and 1 A1g 1Eg()3) transitions [29]. A spectrum of the complex in DMSO shows bands at 13458, 14749 and 23923 cm)1 respectively, associated with a color change from olive to red in solution. This indicates a change of nickel coordination from four (square planar) to six (Oh) with 3A2g(F) 3T2g(F)()1), 3 A2g(F) 3T1g(F)()2) and 3A2g(F) 3T1g(P)()3) transitions [29]. The le values per nickel(II) ion for the complexes [Ni2 L2 Cl2 (H2O)2] 2H2O and [Ni2 L3 Cl2 (H2O)2] 3H2O are 0.6 and 0.8 B.M. which dier from the value found for the complex [Ni2 L1] 2H2O. This could indicate that the coordination geometry is dierent in the two complexes compared with the latter one. Nujol mull electronic spectra of the two complexes showed a broad band in the 1503715748 cm)1 range with a shoulder in the 1302013254 cm)1 range. This suggests distorted trigonal bipyramidal or square pyramidal geometry around the nickel(II) ion [30]. The same absorption peaks are found when the spectra, obtained for DMSO solution of the complexes, dissolve without any color change. This indicates preservation of the ve coordinate conguration in donor solvents. Magnetic moment values for the cobalt(II) complex showed that there is also an antiferromagnetic exchange interaction present. The complex [Co2 L1] 2H2O exhibits a broad band at 18281 cm)1 which is ascribed to the 1A1g 1B1g transition as observed in the case of square-planar cobalt complexes [28]. Solution of the complex in DMSO induces the following color changes: pink violet blue green. The electronic solution spectra were characterized by the appearance of two main bands at 15128 and 16051 cm)1 which can be ascribed to the 4T1g 4A2g(F)()2) and 4T1g 4 T1g(P)()3) transitions of an octahedral geometry. The dd band appearing in the absorption spectra (nujol mull) of the complexes [Co2 L2 Cl2 (H2O)2] 2H2O, [Co2 L3 Cl2 (H2O)2] 3H2O and [Co2 L4 Cl2 (H2O)2] 2 1/2H2O were found to have broad bands at 18050, 17960 and 17985 cm)1 respectively. Such transitions are characteristic of square-pyramidal or distorted trigonal-bipyramidal structures with the 4A2(F) 4A2(P) transition [28]. The complexes dissolve in DMSO with no color change and their absorption bands are shifted to 19607, 19540 and 19230 cm)1 respectively. E.s.r. spectrum The x-band e.s.r. spectrum of the copper complex was recorded on a powder solid at room temperature (Figure 1). It exhibits an axial signal which can be interpreted in terms of tetrahedral species with a strong signal in the low eld region, corresponding to g? 2:19, and a weak signal in the high eld region due to gk 2:06 while the giso is 2.15. Splitting of the signal in the high eld region may be due to a dierence in surroundings between the two copper(II) centers suggesting a binuclear structure for this complex [31]. As shown before, one of them forms a six-membered ring and two ve-membered rings, whereas the other forms only two ve-membered rings. The G value is equal to 0.32, indicating that antiferromagnetic interaction is taking place between the copper(II) ions [32,33]. It is interesting to note that the g? > gk > 2:0023, indicating that the unpaired electron is present in the dxy ground state in a square planar geometry [34]. X-ray powder diraction X-ray patterns of the complexes [Cu2 L1] 2H2O, [Ni2 L1] 2H2O, and [Co2 L1] 2H2O were recorded over the 2h = 0100 range. The principal intraspace lines (d) and their intensities are represented in Table 3 and are shown in Figure 2. Generally, the complexes [Cu2 L1] 2H2O and [Ni2 L1] 2H2O have nearly similar crystallinity which is higher than that of

Fig. 1. X-band powder e.s.r. of the complex [Cu2 L1] 2H2O.

50
Table 3. X-ray powder diraction of the [Cu2 L1] 2H2O, [Ni2 L1] 2H2O and [Co2 L1] 2H2O complexes [Cu2 L1] 2H2O n I 1 2 3 4 5 6 7 8 9 10 11 12 100 70 30 40 25 37 60 85 20 10 12 27 2h 7.465 6.660 5.299 4.811 4.135 4.058 3.750 3.661 3.336 3.213 3.049 2.790 d 11.833 13.261 16.663 18.352 21.351 21.756 23.542 24.114 26.463 27.476 28.953 31.640 Ni2 L1 2H2 O n I 1 2 3 4 5 6 7 8 9 10 11 12 13 100 15 95 25 92 18 58 30 70 50 32 25 10 2h 6.340 5.850 5.351 4.808 4.687 3.986 3.690 3.631 3.553 3.498 2.589 2.348 1.810 d 13.929 15.095 16.502 18.364 18.838 22.149 23.925 24.314 24.847 25.238 34.096 37.595 48.769 [Co2 L1] 2H2O n I 1 2 3 4 5 6 7 8 9 100 10 75 100 10 20 77 10 12 2h 6.368 5.870 5.344 4.688 4.003 3.712 3.563 2.859 1.820 d 13.868 15.044 16.523 18.834 22.055 23.783 24.777 30.877 48.501

Fig. 2. X-ray powder diraction of the Cu(II), Ni(II) and Co(II) complexes of the L1 Schi-bases.

[Co2 L1] 2H2O. Each complex has specic d values, which can be used for its characterization [35]. Thermal analysis The thermal behavior of the complexes has been studied using t.g.a., d.t.g., d.t.a. and d.s.c. analysis. Typical curves are present in Figures 3 and 4. Thermal curves obtained for most of the complexes were very similar in character. The decomposition stages, temperature

ranges, decomposition product, as well as the found and calculated weight loss percentages of the complexes are given in Table 4. The complexes [Cu2 L1] 2H2O, [Ni2 L1] 2H2O and [Co2 L1] 2H2O undergo decomposition mainly in four stages. The rst stage takes place in the 60117, 50223 and 62110C ranges with d.t.g. peaks at 103, 161 and 92C, respectively, corresponding to dehydration and release of two water molecules. The mass loss observed in this step is 6.62, 7.46 and 7.53% against the calculated loss of 7.38, 7.53 and 7.52%, respectively. The dehydration step is associated with endothermic changes in the 107150 and 98166C ranges with d.t.a. peaks at 135C, and in the 155187 and 150196C ranges with d.s.c. peaks at 172C for the complexes [Cu2 L1] 2H2O and [Co2 L1] 2H2O. Dehydration of the complex [Ni2 L1] 2H2O takes place in two steps as shown by the d.t.a. curve (Figure 2) which depicts two endothermic peaks at 96 and 185C in the temperature range 75218C. This indicates that the complex dehydrates in two well separated steps due to the presence of a loosely bound lattice water molecule and more strongly bound one. Also, the formation of hydrogen bonds with the lattice water may raise the dehydration temperature. The wide range of dehydration shown by the t.g. results (50223C) supports this idea. The d.s.c. curve of this complex shows an endothermic peak at

Fig. 3. T.g.a. and d.t.g. of the Cu(II), Ni(II) and Co(II) complexes of the L1 Schi-bases.

51 and [Co2 L1] H2O is in continuation with the second stage in the 328365 and 308324C range with d.t.g. peaks at 351 and 323 C. The mass loss observed is 12.27 and 12.29% against a calculated loss of 12.56 and 12.55% showing that another molecule of CH3COOH is expelled. The third decomposition stage of the complex [Ni2 L1] H2O is shown also by the endothermic peak at 400C (d.t.a. and d.s.c.). The nal decomposition of the complexes with metal formation occurs in the 480670, 507677 and 450652C ranges with d.t.g. peaks at 563, 577 and 550 C, respectively. The t.g. curves of the complexes [Ni2 L2 Cl2 (H2O)2] H2O and [Ni2 L3 Cl2 (H2O)2] 3H2O show a weight loss of 3.5 and 8.96% (calcd. 3.49 and 8.79%) in the temperature ranges 107145 and 122223C with d.t.g. maxima at 126 and 184 C, corresponding to a loss of lattice water. The second decomposition step of the two complexes in the 220290 and 310394C range have d.t.g. peaks at 256 and 352 C. It brings a weight loss of 32.11 and 28.54% (calcd. 32.38 and 27.18%) which correlate with the loss of two molecules of coordinated water, one chlorine molecule and partial decomposition of the ligand with evolution of the carboxylate moiety as acetic acid. Partial decomposition of the complexes is continuing in the 290390 and 394496C ranges with d.t.g. peaks at 348 and 445 C showing weight losses of 21.3 and 11.25% (calcd. 21.34 and 11.41%). The remaining part of the ligands is lost in the 390446 and 496594C range where the nal decomposition takes place at 418 and 545 C with the formation of nickel metal as the nal product. The endothermic peaks obtained in the 135215 and 150260C range with d.t.a. peaks at 162 and 215C for the complexes [Ni2 L2 Cl2 (H2O)2] H2O and [Ni2 L3 Cl2 (H2O)2] 3H2O are associated with the dehydration process. The d.s.c. curves of the complexes have endothermic peaks at 156 and 258C conrming the dehydration processes. Partial decomposition of the complex [Ni2 L2 Cl2 (H2O)2] H2O is indicated by the endothermic peak in the 215383C range which has a maximum at 311 C (d.t.a.). The complex [Ni2 L3 Cl2 (H2O)2] 3H2O has endothermic changes in the 318368C range with two d.t.a. peaks at 341 and 400 C. The rst peak indicates melting of the complex while the second shows partial decomposition. A sharp endothermic peak in the 348351C range with a maximum at 349 C (d.s.c.) supports melting of the complex, while partial decomposition is shown by the endothermic peak in the 386405C range with the d.s.c. maximum at 396C. Final decomposition of the two complexes is shown by exothermic peaks at 551C (d.t.a), 528C (d.s.c.) for the complex [Ni2 L2 Cl2 (H2O)2] H2O and 554 C (d.t.a.), 568 C (d.s.c.) for the complex [Ni2 L3 Cl2 (H2O)2] 3H2O. Thermal decomposition curves of the complexes [Co2 L2 Cl2 (H2O)2] 2H2O, [Co2 L3 Cl2 4 (H2O)2] 3H2O and [Co2 L Cl2 (H2O)2] 2H2O

Fig. 4. D.t.a. calorigrams of the Cu(II), Ni(II) and Co(II) complexes of the L1 Schi-bases. (...) [Cu2 L1] 2H2O,( )[Ni2 L1] 2H2O,() [Co2 L1] 2H2O

239C representing dehydration in the temperature range 217262C. The second decomposition stage of the complexes [Ni2 L1] H2O and [Co2 L1] H2O takes place in the 280328 and 224308C ranges with d.t.g. peaks at 303 and 270C. This step brings weight losses of 16.2 and 16.05% against the calculated losses of 16.12% and 16.11% that correlate with elimination of 1 mol of both CH3COOH and NH3. The d.t.a. curve of the complex [Ni2 L1] H2O has a wide range of thermal change between 308 and 443 C with two endothermic peaks at 334 and 400 C, which correlates with melting and partial decomposition. Melting of the complex is also conrmed by a sharp endothermic d.s.c. peak at 337 C. Endothermic changes were observed for the complex [Co2 L1] H2O in the 276322C range with a d.t.a. peak at 293 C, and in the 283296 range with a d.s.c. peak at 283 C which accompanied partial decomposition of the complex. On the other hand, the complex [Cu2 L1] H2O loses CH3COOH and NH3 in two consecutive steps in the 152200 and 200220C range with d.t.g. peaks at 184 and 208C and mass losses of 11.34 and 3.95% against the calculated losses of 12.31 and 3.48%. This step is followed by a steady mass loss and may be due to the expulsion of the remaining part of the ligand molecule together with volatilization of the residue [36]. This is supported by the endothermic peaks at 213C (d.t.a.) and 217C (d.s.c.) corresponding to melting of the complex, followed by sharp exothermic peaks at 240C (d.t.a.) and 240C (d.s.c.) which represent vaporization following melting [37]. The third decomposition stage of the complexes [Ni2 L1] H2O

52
Table 4. T.g.a. and d.t.g. data of the complexes Complex [Cu2 L1] 2H2O T.g. plateau D.t.g. Mass loss % Process (C) Exp. Calcd. 103 184 208 563 161 303 351 577 92 270 323 550 126 256 348 418 98 302 335 431 184 352 445 545 96 274 377 541 113 335 460 653 6.62 11.34 3.95 7.46 16.2 12.27 41.06 7.53 16.05 12.29 39.29 3.5 32.11 21.3 20.35 6.7 19.51 10.96 39.65 8.96 28.54 11.25 33.66 8.32 27.88 26.92 15.91 7.5 17.13 10.95 7.38 12.31 3.48 7.53 16.12 12.56 39.18 7.52 16.11 12.55 39.14 3.49 32.38 21.34 19.98 6.74 20.02 11.23 39.84 8.79 27.18 11.41 33.44 8.79 27.18 26.87 17.94 7.46 17.73 9.95 Dehydration Partial decomposition Partial decomposition Final decomposition Dehydration Partial decomposition Partial decomposition Final decomposition Dehydration Partial decomposition Partial decomposition Final decomposition Dehydration Partial decomposition Partial decomposition Final decomposition Dehydration Coordination sphere Decomposition Final decomposition Dehydration Coordination sphere Partial decomposition Final decomposition Dehydration Partial decomposition Partial decomposition Final decomposition Dehydration Coordination sphere Partial decomposition Final decomposition Product Residues% and type Exp. Calcd.

60117 152200 200220 480670 Ni2 L1 2H2 O 50223 280328 328365 507677 [Co2 L1] 2H2O 62110 224308 308324 450652 [Ni2 L2 Cl2 (H2O)2] H2O 107145 220290 290390 390446 [Co2 L2 Cl2 (H2O)2] 2H2O 82114 277328 328342 342521 [Ni2 L3 Cl2 (H2O)2] 3H2O 122223 310394 394496 496594 [Co2 L3 Cl2 (H2O)2] 3H2O 76115 247301 311443 450615 [Co2 L4 Cl2 (H2O)2] 2 1/2 H2O 76146 271400 400520 520787 *T.g. curve did not reach plateau at 1000 C.

2H2O CH3COOH NH3 L 2H2O CH3COOH+NH3(0.23L) CH3COOH(0.18L) 0.58L 2H2O CH3COOH+HH3(0.23L) CH3COOH(0.18L) 0.58L 2H2O 2H2O+Cl2+CH3CO2H(0.22L) 0.4L 0.38L 2H2O 2H2O+Cl2 CH3CO2H(0.2L) 0.78L 3H2O 2H2O+Cl2+CH3CO2H(0.2L) 0.2L 0.6L 2 1/2H2O 2H2O+Cl2+CH3CO2H(0.19L) 0.49L 0.32L 2 1/2H2O 2H2O+Cl2 CH3CO2H(0.18L) L

Not complete*

23.01

24.58 Ni

25.16

24.66 Co

22.01

22.77 Ni

22.6

22.07 Co

17.68

19.13 Ni

20.68

19.19 Co

Not complete*

each show a similar sequence of four decomposition steps with elimination of the following species: 1. Lattice water in the 82114, 76115 and 76146C range with d.t.g. peaks at 98, 96 and 113C with mass loss of 6.7, 8.32 and 7.5% respectively, (calcd. 6.74, 8.79 and 7.46%). 2. Two molecules of coordinated water and one molecule of chlorine are evolved in the second decomposition step of the complexes [Co2 L2 Cl2 (H2O)2] 2H2O and [Co2 L4 Cl2 (H2O)2] 2H2O. This step takes place in the 277328 and 271400C range with d.t.g. peaks at 302 and 335C. It has a mass loss of 19.51 and 17.13% against a calculated mass of 20.02 and 17.73%. The second decomposition step of the complex [Co2 L3 Cl2 (H2O)2] 3H2O represents the loss of two coordinated water molecules, one molecule of chlorine in addition to one molecule of acetic acid with a mass loss of 27.88% (calcd. 27.18%). It starts at 247C and ends at 301C with a d.t.g. peak at 274C. 3. Partial decomposition starts with the third step, which follows immediately after the second step in the 328342 and 400520C range, with d.t.g. peaks at 335 and 460C. This step includes separation of one molecule of acetic acid from the complexes [Co2 L2 Cl2 (H2O)2] 2H2O and

[Co2 L4 Cl2 (H2O)2] 2H2O with a mass loss of 10.96 and 10.95% (calcd. 11.23 and 9.95%). For the complex [Co2 L3 Cl2 (H2O)2] 3H2O, its third decomposition step is represented by partial decomposition of the ligand in the 311443C range with a d.t.g. peak at 377C and mass loss of 26.92% (calcd. 26.87). 4. Final decomposition takes place in the 342521, 450615 and 520787C ranges with d.t.g. peaks at 431, 541 and 653C respectively. The d.t.a. and d.s.c. curves of the complexes [Co2 L2 Cl2 (H2O)2] 2H2O, [Co2 L3 Cl2 4 (H2O)2] 3H2O and [Co2 L Cl2 (H2O)2] 2H2O show endothermic peaks within the temperature ranges 93195, 93134 and 105178C, respectively. These peaks have maxima at 148, 134 and 149C which are assigned to dehydration. The d.s.c. curves also indicate dehydration with endothermic peaks at 193, 174 and 198C, respectively. The loss of coordinated water and chloride ions as chlorine gas are shown by the endothermic peaks at 301, 299C (d.t.a.) and 316, 313C (d.s.c.), for the complexes [Co2 L2 Cl2 (H2O)2] 2H2O and [Co2 L4 Cl2 (H2O)2] 2H2O. This fragment was lost in addition to decarboxylation as acetic acid in one step for the complex [Co2 L3 Cl2 (H2O)2] 3H2O as indicated by the endother-

53 From the d.t.a. curves, the reaction order n and S activation energy DEa of the thermal decomposition have been elucidated using the Piloyan formula [38].
ln t C Ea =RT

Fig. 5. ln t versus 1000/T relationship for the complex [Co2 L4 Cl2 (H2O)] 2 H2O

mic peak at 300C (d.t.a.); 301 and 339C (d.s.c.). The exothermic peaks at 483C (d.s.c.); 557C (d.t.a.), 559C (d.s.c.); and 564C (d.t.a.) show nal decomposition of the complexes.

The plot of ln t versus 1000/T gave a straight line with slope )Ea/RT (Figure 5). The obtained values are given in Table 5. The order of the decomposition for all complexes is unity. The activation energy values for the dehydration processes for all complexes are more than the activation energy values for the removal of lattice water [39]. The activation energy values for the Cu(II), Ni(II) and Co(II) complexes are expected to increase proportionally to the decrease in their radius [40]. The activation energies of the dehydration step of the complexes [Cu2 L1] 2H2O, [Ni2 L1] 2H2O and [Co2 L1] 2H2O which have square-planar structure decrease proportionally to their radius degrees. DEa values for these complexes are 91, 88 and 85 J/mol. The shorter the radius of the metal ion, the easier the ligand approaches the central atom. As a result, metalligand interaction becomes stronger, the detachment of the link more difcult, and DEa values increase [41, 42]. It is shown in Table 3, that the Ni complexes are the most stable, no matter what Schi-base ligand is present. It should be also emphasized that Ni com-

Table 5. D.t.a. and d.s.c. data of the complexes. Complex [Cu2 L1] 2H2O Temp. range t(C) 107150 200225 235251 458700 75218 308443 444663 98166 276322 500647 135215 215383 426629 93195 202360 DTA peak t(C) 135 endo 213 endo 241 exo 570 exo 96 endo 185 endo 334 endo 400 endo 524 exo 135 endo 293 endo 568 exo 162 endo 311 endo 551 exo 148 endo 301 endo S Ea J/mol 91 148 291 107 88 83 257 399 78 85 100 82 191 46 73 248 Temp range t(C) 155187 204226 234245 217262 323350 397419 545577 150196 283296 572591 176207 500562 165215 308323 344354 478491 215290 348351 386405 560586 127195 296305 338342 550570 176223 299323 333338 DSC peak t(C) 172 endo 217 endo 240 exo 239 337 400 554 172 283 572 195 528 193 316 348 483 258 349 396 568 174 301 339 559 198 313 334 DH J/g 157 32 89 40 56 350 )343 142 75 )492 156 )343 205 335 76 )456 181 92 304 )326 218 91 242 )549 208 184 77 Process

0.96 1.05 0.67 0.85 1.03 0.88 1.08 1.0 0.81 1.0 1.0 1.02 1.6

Ni2 L1 2H2 O

[Co2 L1] 2H2O

[Ni2 L2 Cl2 (H2O)2] H2O

endo endo endo exo endo endo exo endo exo endo endo endo exo endo endo endo exo endo endo endo exo endo endo endo

[Co2 L2 Cl2 (H2O)2] 2H2O

[Ni2 L3 Cl2 (H2O)2] 3H2O

150260 318368 500629 93134 287323 469607 105178 289316

[Co2 L3 Cl2 (H2O)2] 3H2O

215 341 400 554 134 300

endo endo endo exo endo endo

0.81 0.86 1.0 1.0 0.88 1.2 1.05 0.86

49 284 422 74 47 398 70 51 424 70

[Co2 L4 Cl2 (H2O)2] 21/2H2O

557 exo 149 endo 299 endo 564 exo

Dehydration Melting Vaporization Final decomposition Dehydration Dehydration Melting Partial decomposition Final decomposition Dehydration Partial decomposition Final decomposition Dehydration Partial decomposition Final decomposition Dehydration Coordination sphere Partial decomposition Final decomposition Dehydration Melting Partial decomposition Final decomposition Dehydration Coordination sphere Partial decomposition Final decomposition Dehydration Coordination sphere Partial decomposition Final decomposition

54

It was conrmed by heating the complex at 190C where its i.r. spectrum shows that the )NH vibrations have completely disappeared. Also, the bands at 1587 and 1429C attributed to the presence of the carboxylate group are completely lost at 220C, indicating its decomposition and evolution as CH3COOH. This mechanism is also applied in the case of [Ni2 L1] 2H2O and [Co2 L1u] 2H2O. Heating complex [Cu2 L1] 2H2O induces thermochromism with color changes which support the abovementioned mechanism:
Cu2 C13 N4 O6 H16 2H2 O 150 C ! bright green Cu2 C13 N4 O6 H16 2H2 O olive green Cu2 C13 N4 O6 H16 190 C ! Cu2 C11 N4 O4 H12 CH3 COOH brown Cu2 C11 N4 O4 H12 220 C ! Cu2 C11 N3 O4 H9 NH3 deep brown

Fig. 6. I.r. spectrum of the complex [Cu2 L1] 2H2O heated at different temperatures.

plexes are more stable than its analogous isostructural Cu and Co complexes (Figure 5). The high stability of Ni complexes may be due to strong hydrogen bonding to the other water molecules and oxygen atom of the neighboring carboxylate group [43] which reect the high dehydration temperature of the Ni complexes. Also, Ni complexes may exist as polymeric structure. In an attempt to elucidate the mechanism of the thermal decomposition mechanism of the complexes, the i.r. spectra of the [Cu2 L1] 2H2O; [Ni2 L1] 2H2O and [Co2 L1] 2H2O complexes heated at 150, 190, 220C; 200, 350, 400C and 180, 300, 410C respectively, were recorded (Figure 6, is an example). It shows that the i.r. spectrum changes shape, intensity and position of some characteristic bands. At 150C, the i.r. spectrum of the complex indicates that bands at 3400, 3232 and 3082 cm)1 assigned to the )OH and )NH suer broadening and become less intense compared to its i.r. spectrum at room temperature. This can be explained by the formation of the hydrogen bond NH O which changes to N HO. This mechanism can be represented as follows:

The same phenomenon was observed with [Ni2 L1] 2H2O:

Based on the above analytical data and physicochemical properties, a square planar structure was proposed for the binuclear complexes of the L1 Schi-base in which the metal ion is coordinated through the azomethine nitrogens, the amide groups and the carboxylate oxygen. For the binuclear complexes of L2, L3 and L4 Schi-base, a ve coordinated structure is suggested in which the metal atom is coordinated to the enol and carboxylate oxygens: the azomethine and amide nitrogens.

55
18. R.C. Mehrotra and R. Bohra, Metal Carboxylates, Academic Press, New York, 1983. 19. A.V.R. Warrier and R.S. Krishnan, Spectrochim. Acta, A27, 1243 (1971). 20. M. Kato, H.B. Jonassen and C.J. Fanning, Chem. Rev., 64, 99 (1964). 21. F.A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, Wiley Eastern, New Delhi, 1972. 22. E.J. Halbert, C.M. Harris, E. Sinn and G.J. Sulton, Aust. J. Chem., 26, 951 (1973). 23. S.J. Gruber, C.M. Harris and E. Sinn, Inorg. Chem., 7, 268 (1968). 24. S.J. Gruber, C.M. Harris and E. Sinn, J. Inorg. Nucl. Chem., 30, 1805 (1968). 25. S.J. Gruber, C.M. Harris and E. Sinn, Inorg. Nucl. Chem. Lett., 3, 495(1967); 4, 107 (1968). 26. J. Bjerrum, C.J. Ballhausen and C.K. Jrgensen, Acta Chem. Scand., 8, 1275 (1954). 27. E.F. Hasty, L.J. Wilson and D.N. Hendrickson, Inorg. Chem., 17, 1834 (1978). 28. A.B.P. Lever, Inorganic Electronic Spectroscopy, 2nd edn., Elsevier, Amsterdam, 1984. 29. Y. Nishida and S. Kida, Coord. Chem. Rev., 27, 275 (1979). 30. A.P.B. Lever, J. Inorg. Nucl. Chem., 27, 149 (1965). 31. S.S. Tandon, L.C. Laurence, K. Thompson, S.P. Connors and J.N. Bridson, Inorg. Chem. Acta, 213, 289 (1993). 32. A.S. El-Tabl, Polish J. Chem., 71, 1213 (1997). 33. A.S. El-Tabl, J. Chem. Res., 19, (2004). 34. B.A. Goodman and J.B. Raynor, Adv. Inorg. Chem. Radiochem., 13, 136 (1970). 35. E.R. Souaya, W.G. Hanna, E.H. Isamil and N.E. Milad, Molecules, 5, 1121 (2000). 36. J.A. Dean (Ed.), Langs Hand Book of Chemistry, 13th edn., McGraw-Hill, New York, 1967. 37. A.S. El-Tabl and M.M. Abou-Sekkina, Pol. J. Chem., 73, 1937 (1999). 38. G.O. Piloyan, I.D. Ryabchikov and O.S. Novikova, Nature, 5067, 1229 (1966). 39. K.K. Mohammed Yusu and R. Sreekala, Thermochim. Acta, 179, 313 (1991). 40. H. Arslan, N. Ozpozan and N. Tarkan, Thermochim. Acta, 383, 69 (2002). 41. H. Sangari and G.S. Sodhi, Thermochim. Acta, 171, 149 (1990). 42. M.L. Kantouri, G.A. Katsoulos, C.C. Hadjikostas and P. Kokorotsikos, J. Therm. Anal., 35, 2411 (1989). ` 43. Z. Vargova, V. Zeleoak, I. C saova and K. Gyoryova, Thermo chim. Acta, 423, 149 (2004).

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