investigations on some hetero-trinuclear complexes of

Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry

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INVESTIGATIONS ON SOME HETERO-TRINUCLEAR COMPLEXES OF NICKEL(II) AND COPPER(II) Orhan Atakol , Sefa Durmus , Zehra Durmus , Cengiz Arici & Burhanettin Çiçek To cite this article: Orhan Atakol , Sefa Durmus , Zehra Durmus , Cengiz Arici & Burhanettin Çiçek (2001) INVESTIGATIONS ON SOME HETERO-TRINUCLEAR COMPLEXES OF NICKEL(II) AND COPPER(II), Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 31:9, 1689-1704, DOI: 10.1081/SIM-100107713 To link to this article: http://dx.doi.org/10.1081/SIM-100107713

Published online: 15 Aug 2006.

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Date: 06 January 2016, At: 05:49

SYNTH. REACT. INORG. MET.-ORG. CHEM., 31(9), 1689±1704 (2001)

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INVESTIGATIONS ON SOME HETEROTRINUCLEAR COMPLEXES OF NICKEL(II) AND COPPER(II) Orhan Atakol,1 Sefa Durmus,*,1 Zehra Durmus,1 Cengiz Arici,3 and Burhanettin CËicËek2 1

Department of Chemistry and Department of Chemical Engineering, Faculty of Sciences, University of Ankara, Ankara, Turkey 3 Department of Engineering Physics, Faculty of Engineering, University of Hacettepe, Ankara, Turkey

2

ABSTRACT Ni(II) and Cu(II) complexes of N,N0 -bis(salicylidene-1,3-diaminopropane) were prepared and found to form linear and non-linear trinuclear complexes. Elemental analyses, IR spectroscopy, thermogravimetry and X-ray diraction techniques applied to the complexes yielded valuable information about their moleculer structures. It was observed that m-bridges in these trinuclear complexes form through the phenolic oxygens of the ligand or through anions present in the medium. In the presence of acetate, nitrate or nitrite,

*Corresponding author. E-mail: [email protected]

1689 Copyright # 2001 by Marcel Dekker, Inc.

www.dekker.com

1690

ATAKOL ET AL.

m-bridges form between a pair of atoms resulting in linear trinuclear complexes. However, the presence of chloride or bromide results in m-bridges involving the phenolic oxygens of N,N0 -Bis(salicylidene)-1,3-diaminopropane.


INTRODUCTION N,N0 -Bis(salicylidene)-1,3-diaminopropane (1) has been reported in the coordination chemistry literature for about ®fty years, and is a thoughtprovoking ligand175. Holm described the preparation of a paramagnetic nickel complex of the said ligand in detail. It is interesting to note that in 1960, the very same complex was claimed to be diamagnetic6. It was only after 1985 that this paradox was resolved. The explanation was that when nickel(II) acetate was used in the complex preparation, a green-coloured paramagnetic complex (2) forms, however, a brown-coloured diamagnetic complex (3) forms only when NiCl2 or NiSO4 was used at a pH greater than 9. In addition to this rationalization, the trinuclear structure of complex (2) in Fig. 1 was also identi®ed after 19904,5,7. RESULTS AND DISCUSSION In this study, complexes similar to complex (2), with a dierent central metal atom were prepared and the molecular structures were identi®ed by elemental analyses, IR spectroscopy and thermogravimetric analysis as well as X-ray crystallography. Complexes (5)7(9) were prepared as shown in Fig. 2 and used as a starting material for the nickel complexes (3). Similar trinuclear complexes were also prepared with copper complex (4), shown in Fig. 3. In this communication, instead of a lengthy molecular representation, a shorthand notation, L was used for the dianion of the ligand such that the complexes (3) and (4) are named NiL and CuL, respectively. Formation of hetero-trinuclear complexes was observed when acetates, nitrates, nitrites or halides of divalent metal ions were used as the transition metal salts, while no trinuclear complex was found to form when sulphates, chlorates or perchlorates were utilized. In a similar eort with Fe(III) and Cr(III), no polynuclear complexes were isolated. When the metal salt was either acetate, nitrate or nitrite, these ions were observed to coordinate with the complex and via an m-bridge. In such a case all three metal atoms are in a linear arrangement. On the other hand, when the metal salt was either chloride or bromide, a m-bridge forms and the M-M0 -M (M Cu, M0 Pb or Cd) angles were observed to deviate from 180 .


HETERO-TRINUCLEAR COMPLEXES

Figure 1.

1691

Structure of trinuclear Nickel(II) complex.

The General Reaction Mechanism The general reaction mechanism for the complexes prepared is given in Fig. 2. Similar complexes were prepared with CuL and acetate salts and the stoichiometries presented in Fig. 4 were obtained, when M represents Cd(II), Mn(II) or Co(II). Fig. 5 presents the general reaction scheme for the hetero-trinuclear complexes prepared from CuL, with CdBr2 or PbCl2 in dioxane as solvent. Analytical and Geometrical Results A complete listing of the complexes isolated in the solid form, together with their corresponding stoichiometries are presented in Table I. The given stoichiometries were con®rmed by the elemental analyses results as well as a molecular model of the CuLPbCl2CuL complex (16) generated via X-ray crystallography and by the references cited therein. Among these, we were not able to obtain, reliable and reproducable elemental analysis data for


1692

Figure 2.

ATAKOL ET AL.

Reaction mechanism for the heteronuclear complex obtained with NiL

Figure 3.

Structure of CuL (4).



Figure 4. CuL

1693

Reaction mechanism for the linear heteronuclear complexes formed with

complex (10), thus no data are given for C and H. This might be explained by the fact that while a pair of DMF molecules coordinate with the complex structure, additional DMF molecules enter into the crystals as solvent. These solvent DMF molecules gradually evaporate after ®ltration degrading the crystal structure. However, these crystals, may be kept undegraded for 24 to 36 h. In this study, coating with light hydrocarbon oil of complex (10), resulted in a succesfull X-ray crystall structure determination and the molecular structure shows an extra pair of DMF molecules in the unit cell. Even so, the crystal data is as yet not fully reliable. In addition to this, the nitrogen contents of DMFNiLCo(NO3)2NiLDMF (11) and of

Figure 5. bond.

General reaction mechanism for the CuL complexes with the Cu-M-Cu

(9)

(8)

(7)

(6)

(5)

Comp. No DMFNiLMn(OAc)2NiLDMF C44H50N6O10MnNi2 DMFNiLCu(OAac)2NiLDMF C44H50N6O10CuNi2 DMFNiLCd(OAc)2NiLDMF C44H50N6O10CdNi2 DMFNiLZn(OAc)2NiLDMF C44H50N6O10ZnNi2 DMSONiLMn(OAc)2NiLDMSO C42H50N4O10S2MnNi2

Shortened Stoichiometric Formula

151

153

1887192

1007.39

1007.07

159

1005.54

1054.42

153

996.94

Formula Decomp. Weight Temp. ( C) H

N

M

M

0

49.91 5.34 5.91 11.72 5.56 (50.09) (5.00) (5.56) (11.65) (5.45)

52.19 5.64 8.17 11.93 6.62 (52.46) (5.20) (8.33) (11.65) (6.49)

50.37 5.39 7.88 10.97 10.71 (50.12) (4.97) (7.96) (11.13) (10.66)

52.96 5.38 8.47 11.59 6.26 (52.55) (5.21) (8.35) (11.67) (6.31)

53.16 5.37 8.52 11.29 5.39 (53.04) (5.25) (8.42) (11.77) (5.51)

C

M*

7

7

7

7

7

X

15.77 (15.49)

14.68 (14.49)

14.01 (13.85)

14.27 (14.51)

14.37 (14.64)

Obs. (Calc.)

% Loss of DMF at Decomp. Temp.

Elemental Analysis %, Found (Calculated)

Table I. Elemental Analysis Data of the Prepared Complexes


8

7

Ref. No

1694 ATAKOL ET AL.

DMFNiL1148.94 Mn(NO3)2NiLDMF2DMF C46H60N10O14MnNi2 DMFNiL1007.94 Co(NO3)2NiLDMF C40H46N8O12CoNi2 974.93 DMFNiLCo(NO2)2NiLDMF C40H46N8O10CoNi2 918.12 CuLCd(OAc)2CuL C38H38N4O8CdCu2 CuLMn(OAc)2CuL 860.65 C38H38N4O8MnCu2 959.92 CuLCdBr2CuL C34H32N4O4Br2CdCu2 965.84 CuLPbCl2CuL C34H32N4O4Cl2PbCu2 390

390

370

6.21 (6.09) 6.52 (6.50) 5.87 (5.83) 5.84 (5.79)

13.71 (13.84) 14.69 (14.67) 5.87 (13.23) 13.21 (13.15)

7

7

7

12.35 7 (12.24) 6.04 7 (6.38) 12.19 16.51 (11.71) (16.64) 21.37 7.17 (21.45) (7.35)

49.76 (49.71) 53.47 (53.03) 42.25 (42.54) 42.12 (42.28)

371

4.54 (4.17) 4.31 (4.45) 3.57 (3.36) 3.38 (3.31)

49.12 4.91 8.83 12.19 6.11 (49.28) (4.75) (11.48) (12.03) (6.04)

8.26 11.13 5.09 (9.74) (10.21) (4.78)

154

7

47.18 4.86 8.59 12.01 5.38 (47.65) (4.59) (11.11) (11.64) (5.45)

7

1497151

1007150

*The cores of the trinuclear complexes, M-M0 -M are de®ned as M and M0 .

(16)

(15)

(14)

(13)

(12)

(11)

(10)


7

7

7

7

15.14 (14.97)

14.54 (14.48)

24.38 (25.41)

10

9

HETERO-TRINUCLEAR COMPLEXES 1695

1696

ATAKOL ET AL.


Table II. Final Atomic Coordinates and Equivalent Isotropic Thermal Parameters for Non-Hydrogen Atoms Atom

x

Pb Cu1 Cu2 Cl1 Cl2 O1 O2 O3 O4 N1 N2 N3 N4 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26a C26b

0.64360(2) 0.36819(6) 0.45251(6) 0.7280(2) 0.8491(2) 0.6238(3) 0.4917(3) 0.5583(3) 0.4041(3) 0.4543(5) 0.2692(4) 0.3474(4) 0.1869(4) 0.7161(5) 0.8458(5) 0.9412(6) 0.9109(6) 0.7874(6) 0.6862(6) 0.5582(6) 0.3349(6) 0.2446(6) 0.1774(6) 0.2186(5) 0.2821(5) 0.4158(5) 0.4674(5) 0.3913(6) 0.2588(6) 0.2073(6) 0.3163(5) 0.3576(6) 0.2681(7) 0.1349(6) 0.0939(6) 0.1822(5) 0.1287(5) 0.1068(6) 0.1018(9) 0.170(2)

y 0.25457(2) 0.28905(6) 0.14476(6) 0.4835(2) 0.0995(2) 0.2133(4) 0.0865(3) 0.3000(4) 0.3200(3) 0.1887(4) 0.0829(4) 0.2998(5) 0.2391(4) 0.2420(5) 0.2654(5) 0.3000(6) 0.3109(6) 0.2857(6) 0.2506(5) 0.2274(5) 0.1819(6) 0.0824(6) 0.0992(6) 0.0338(5) 0.0076(5) 0.0313(5) 0.0037(5) 0.0607(5) 0.0823(5) 0.0501(6) 0.3437(5) 0.3982(5) 0.4255(5) 0.3987(6) 0.3449(6) 0.3154(5) 0.2575(5) 0.1804(6) 0.2518(8) 0.173(2)

z 0.22911(1) 0.42210(4) 0.06158(4) 0.1838(1) 0.2818(2) 0.0549(3) 0.1827(2) 0.4052(2) 0.2873(2) 0.0743(3) 0.0938(3) 0.5599(3) 0.4214(3) 0.0208(4) 0.0100(4) 0.0867(4) 0.1777(4) 0.1898(4) 0.1127(4) 0.1322(4) 0.1175(5) 0.0750(4) 0.0245(4) 0.1755(4) 0.2560(4) 0.2558(4) 0.3380(4) 0.4159(4) 0.4173(5) 0.3382(5) 0.2302(4) 0.1390(4) 0.0787(4) 0.1077(5) 0.1948(4) 0.2585(4) 0.3491(4) 0.5082(4) 0.5901(6) 0.599(1)

Beq =AÊ2 2.399(3) 2.51(1) 2.55(1) 5.05(4) 5.92(4) 3.18(8) 2.85(7) 2.95(8) 2.62(7) 3.08(9) 2.92(9) 3.3(1) 3.10(9) 2.5(1) 3.2(1) 3.8(1) 4.0(1) 3.8(1) 2.8(1) 3.2(1) 4.5(1) 3.8(1) 3.9(1) 3.1(1) 2.8(1) 2.6(1) 3.0(1) 3.4(1) 3.8(1) 3.8(1) 2.6(1) 3.4(1) 4.1(1) 4.4(1) 3.9(1) 3.1(1) 3.1(1) 4.0(1) 3.7(2)* 3.3(3)*

HETERO-TRINUCLEAR COMPLEXES Table II.


Atom C27 C28 C29 C30 C31 C32 C33 C34

1697

Continued

x

y

z

0.2267(6) 0.4352(5) 0.5690(5) 0.6469(6) 0.7789(6) 0.8361(5) 0.7623(5) 0.6269(5)

0.2596(8) 0.3475(5) 0.3778(5) 0.4280(5) 0.4495(5) 0.4202(5) 0.3723(5) 0.3487(5)

0.6267(4) 0.5980(4) 0.5547(4) 0.6105(4) 0.5787(4) 0.4871(4) 0.4298(4) 0.4619(3)

Beq =AÊ2 5.4(2) 3.0(1) 2.5(1) 3.1(1) 3.3(1) 3.1(1) 2.9(1) 2.4(1)

C26 atom disordered. P P C26a is an occupancy of 0.7 and C26b has 0.3. Beq 8p2 =3 i j Uij ai aj ai a

DMFNiLCo(NO2)2NiLDMF (12), as shown in Table I, are far from the calculated values. The likely reason for this inconsistency might be the classical Kjeldahl method applied for nitrogen analysis. In this method, weighed complexes are left in hot, concentrated H2SO4 for digestion. During the digestion process, nitrate and nitrite groups are degraded and detach from the structure, causing a reduced nitrogen content for the complexes. Crystal data of the complex (16) are given in Table II, and the atomic coordinates and some selected bond distances are presented in Table III. Fig. 6 shows the ORTEP12 drawing for the molecular structure. The molecular structures of the complexes (5), (7) and (12) have been reported elsewhere5,8,9. Their stoichiometries are as follows: DMFNiL Mn(OAc)2NiLDMF (5), DMFNiLCd(OAc)2NiLDMF (7), DMFNiL Co(NO2)2NiLDMF (12). All three metal atoms are in an octahedral coordination in the respective complexes. The Ni(II) ions bonded by an N2O4 the system while the Mn(II) and Cd(II) ions are coordinated the six oxygens. Three neighbouring octahedra with linearly lined up metal atoms form the molecular structure. As shown in Figs. 2 and 5, CuL and NiL behave as Lewis bases and complete the coordination of the central atom in the absence of acetate, nitrate, nitrite or halides in the solvent. Complex (13) has the CuLCd(OAc)2CuL stoichiometry and, as reported in the literature10, the metal ions in Cu-Cd-Cu are linearly arranged. In this complex Cu ions are in a square-pyramidal geometry while Cd is in an octahedral coordination. Thus, the ®nal polyhedron chain is a square-pyramidal-octahedral-square-pyramidal structure. It may be concluded at this point that, if the central metal ion is of the type preferring octahedral coordination, trimeric structures will be observed.

1698

ATAKOL ET AL.


Table III. Pb-Cl1 Pb-Cl2 Pb-O1 Pb-O3 Pb-O4 Cl1-Pb-Cl2 Cl1-Pb-O1 Cl1-Pb-O3 Cl1-Pb-O4 Cl2-Pb-O1 Cl2-Pb-O3 Cl2-Pb-O4 O1-Pb-O3 O1-Pb-O4 O3-Pb-O4 O3-Cu1-O4 O3-Cu1-N3

2.726(2) 2.838(2) 2.625(4) 2.601(3) 2.533(3) 111.43(6) 94.85(9) 91.67(9) 94.04(9) 107.55(9) 90.99(9) 141.35(8) 156.4(1) 98.3(1) 58.6(1) 81.9(1) 92.0(2)

Bond Distances (AÊ) and Angles ( ) Cu1-O3 Cu1-O4 Cu1-N3 Cu1-N4 O3-Cu1-N4 O4-Cu1-N3 O4-Cu1-N4 N3-Cu1-N4 O1-Cu2-O2 O1-Cu2-N1 O1-Cu2-N2 O2-Cu2-N1 O2-Cu2-N2 N1-Cu2-N2 Pb-O1-Cu2 Pb-O1-C1

1.923(3) 1.912(3) 1.965(4) 1.962(4) 164.8(2) 165.1(2) 92.2(2) 96.9(2) 79.6(2) 91.8(2) 169.1(2) 166.5(2) 92.1(2) 97.6(2) 106.8(1) 123.8(3)

Cu2-O1 Cu2-O2 Cu2-N1 Cu2-N2 Cu2-O1-C1 Cu2-O2-C13 Pb-O3-Cu1 Pb-O3-C34 Cu1-O3-C7 Pb-O4-C34 Pb-O4-Cu1 Cu1-O4-C18 Cu2-N1-C7 Cu2-N1-C8 Cu2-N2-C10 Cu2-N2-C11

1.926(4) 1.917(4) 1.973(5) 1.988(4) 129.3(4) 130.1(3) 104.4(2) 126.4(3) 127.2(3) 107.4(1) 123.4(3) 127.4(3) 123.3(4) 122.2(3) 120.7(3) 123.8(4)

Therefore, the central polyhedron will always be an octahedron. In addition, trimeric structures have never been observed to form with metal ions which do not prefer octahedral coordination, such as palladium(II) and platinum(II). The metal atoms on both sides of the central atom in the complexes with trimeric structures are in their own prefered coordinations. That is, Ni(II) ions in the complexes (5), (6), (7), (8), (9), (10), (11) and (12) are in octahedral coordination, Cu(II) ions in the complexes (13) and (14) are in a square-pyramidal coordination and the complexes (15) and (16) are in a squashed-tetrahedral coordination. These are the most commonly encountered coordinations for Ni(II) and Cu(II) ions11. Infrared Spectroscopy The groups with their respective IR frequencies are presented in Table IV. The aliphatic C-H vibrational bands at 285172930 cm 1 belong to the methyl and methylene groups. The SO vibrational bands at 1068 cm 1 belong to DMSO in the complex (9) and NO vibrational band at between 141871421 cm 1 belong to NO2 and NO3 groups in the complex (10), (11), (12).



Figure 6.

1699

A perspective view of complex (16).

EXPERIMENTAL Apparatus IR spectra were acquired using a Mattson 1000 FTIR spectrophotometer by preparing KBr discs of the sample (5710%). Microanalyses for carbon, hydrogen and nitrogen were performed using a LECO 1000 analyser and additional nitrogen analyses made by classical Kjeldahl method. Chlorine and bromine were quanti®ed by precipitating as silver salts and the metals were analysed using a Hitachi 8200 atomic absorption spectrometer. The crystal data of complex (16) were collected on an Enraf Nonius CAD4 diractometer with Mo-Ka radiation. The crystal and experimental data of the complex (16) are presented in Table V.

1700

ATAKOL ET AL. Table IV.

IR Spectroscopic Data Obtained in KBr Discs (cm 1) IR Data


Comp No. (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16)

C-H (arom.)

C-H (Aliph.)

CO

CN

NO

SO

3055 m73027 m 2930 s72860 m 1651 1634 s 7 7 3054 m73028 m 2928 s72855 m 1652 s 1639 s 7 7 3055 m73026 w 2927 s72876 m 1651 s, 1676 s 1635 s 7 7 3054 m73025 m 2926 s72851 m 1651 s 1634 s 7 7 3058 m73029 w 2927 s72854 m 1646 s 1636 s 7 1068 m 3049 w73025 w 2925 m72858 w 1651 s 1634 s 1419 s 7 3047 w73028 w 2925 m72853 m 1652 s 1637 s 1421 s 7 3049 w73026 w 2925 s72856 s 1651 s 1635 s 1418 s 7 3051 w73028 w 2920 s72855 m 1644 s 1629 s 7 7 3050 w73029 w 2915 s72855 m 1648 s 1634 s 7 7 3053 w73029 w 2921 s72851 m 7 1636 s 7 7 3055 m73028 w 2927 s72859 m 7 1626 s 7 7

Chemicals Salicylaldehyde (99%), 1,3-diaminopropane (for synthesis), dimethylformamide, dioxane, methanol, ethanol, and metal salts [nickel(II) acetate tetrahydrate, nickel(II) chloride hexahydrate, copper(II) acetate monohydrate, copper(II) chloride dihydrate, cobalt(II) acetate tetrahydrate, cobalt(II) nitrate hexahydrate, cobalt(II) chloride hexahydrate, manganese(II) acetate tetrahydrate, manganese(II) nitrate tetrahydrate, manganese(II) chloride tetrahydrate, cadmium(II) acetate dihydrate and cadmium(II) bromide tetrahydrate, zinc(II) acetate dihydrate and sodium nitrite] were purchased from Merck AG and used without puri®cation. Lead(II) chloride was prepared from lead(II) nitrate and sodium chloride by precipitating in an aqueous solution. N,N0 -Bis(salicylidene)-1,3-diaminopropane (H2L) The compound was synthesized using known general condensation reaction13. A quantity of 0.04 mol (4.88 g) of salicylaldehyde was dissolved in 50 mL of hot ethanol. 1,3-Diaminopropane (1.48 g, 0.02 mol) was added to this solution and the mixture was heated to its boiling point. The solution was then set aside for 374 h at room temperature and the resulting yellow crystals were ®ltered and dried in air, m.p. 59760 C. The yield was 5.40 g (95%).


1701


Table V. Crystal and Experimental Data Formula: C34H32N4O4Cl2Cu2Pb Formula weight 965.835 Crystal system: triclinic Space group: P1 Z 2 A 10:231011A B 11:161312A C 14:372112A a 85:5922 b 79:3483 g 87:4792 3 V 1607:47A Dx 1:995 g=cm3 mMoKa 6.792 mm 1 ymax 25:69 T 295K Black F0 0 0 940 Crystal size: 0.20 0.15 0.10 mm Radiation Mo Ka (0.71073 A) R 0:027 Rw 0:033 D=s 0:0009 3 Drmax 0:773 eA 3 Drmin 0:234 eA No. of reflection used 4836 No. of parameters 423 Goodness-of-fit 0.93 Measurements: Enraf Nonius CAD-4 diffractometer Program system: CAD-4 EXPRESS Software Structure determination: MolEN Treatment of Hydrogen Atoms: H atoms bonded to C atoms were placed geometrically 0.95 AÊ from their parent atoms and a riding model was used for all H atoms. Refinement: full matrix least-squares (MolEN)

Preparation of NiL (3) A quantity of 0.01 mol (2.82 g) of N,N0 -bis(salicylidene)-1,3-diaminopropane was dissolved in 30 mL hot ethanol and 10 mL of ammonia (20%) were added to this solution. Then a solution of NiCl26H2O (2.38 g, 0.01 mol) in 30 mL hot water was added. After setting the solution aside for

1702

ATAKOL ET AL.

an hour, the precipitated light green Ni(II) complex was ®ltered and ovendried at 140 C for 2 h. The brown complex was recrystallized from ethanoldioxane (1:1); m.p. > 330 C, yield 3.08 g (90%).


Preparation of CuL (4) This complex was prepared similar to NiL from N,N0 -bis(salicylidene)-1,3-diaminopropane and CuL22H2O. The dark green complex was recrystallized from ethanol and oven-dried at 80 C, m.p. > 330 C, yield 3.03 g (88%). Preparation of m-Acetato-Bridged Nickel Complexes (5)7(9) A quantity of 0.001 mol (0.340 g) of complex (3) (NiL) was dissolved in 50 mL hot DMF and the temperature was gradually raised to 110 C. For complexes (5) and (9), 0.0005 mol (0.123 g) of Mn(OOCCH3)24H2O; for complex (6) 0.0005 mol (0.100 g) of Cu(OOCCH3)2H2O; for complex (7), 0.0005 mol (0.150 g) of Cd(OOCCH3)24H2O and for complex (8). 0.0005 mol (0.112 g) of Zn(OOCCH3)22H2O were dissolved in 20 mL methanol and mixed with the above solution. The resulting mixture was set aside for 273 days at room temperature. The precipitated crystals were ®ltered and dried in air. The yields for the complexes were 0.34 g (68%), 0.39 g (76%), 0.27 g (51%), 0.40 g (79%), and 0.39 g (77%), respectively. For complex (9), DMSO was used instead of DMF. Preparation of m-Nitrato- and m-Nitrito-Bridged Nickel Complexes, (10), (11) and (12) A quantity of 0.001 mol (0.339 g) of complex (3) (NiL) was dissolved in 50 mL hot DMF and the temperature was raised to 100 C. For complex (10), 0.0005 mol (0.100 g) of MnCl24H2O and 0.001 mol (0.085 g) of NaNO3; for complex (11) 0.0005 mol (0.120 g) of CoCl26H2O and 0.001 mol (0.085 g) of NaNO3, for complex (12), 0.0005 mol (0.12 g) of CoCl26H2O and 0.001 mol (0.070 g) of NaNO2 were dissolved in 30 mL of a hot methanol-water mixture (2:1) and added to the above solution. The resulting mixture was set aside for 36748 h at room temperature. The resulting precipitates were ®ltered, washed with Et2O and dried in air. The yields of the complexes were 0.25 g (33%), 0.27 g (50%) and 0.32 g (66%), respectively.


1703

Preparation of m-Acetato-Bridged Copper Complexes (13) and (14)


A quantity of 0.001 mol (0.344 g) of complex (4) (CuL) was dissolved in 50 mL of hot dioxane and heated to its boiling point. For complex (13), 0.0005 mol (0.150 g) of Cd(OOCCH3)24H2O and for complex (14), 0.0005 mol (0.239 g) of Mn(OOCCH3)24H2O were dissolved in 20 mL hot methanol and mixed with the above solution. The ®nal mixtures were set aside for 576 days at room temperature. The formed green crystals were ®ltered and oven-dried at 110 C. Yields were 0.145 g (32%) for (13) and 0.198 g (46%) for (14). Preparation of Copper Complexes (15) and (16) A quantity of 0.001 mol (0.344 g) of complex (4) (CuL) was dissolved in 50 mL dioxane-DMF (3:1) mixture. For complex (15), 0.0005 mol (0.175 g) of CdBr24H2O and for complex (16), 0.0005 mol (0.140 g) of PbCl2 were dissolved in 10 mL hot water and added to the above solution. The ®nal mixtures were set aside for 576 days at room temperature. The precipitated crystals were ®ltered and oven-dried. Yields were 0.142 g (30%) for complex (15) and 0.108 g (23%) for complex (16).

ACKNOWLEDGMENT The authors were grateful for the support given by Ankara University Research Fund (Project no: 96.25.00.005).

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ATAKOL ET AL.

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Received October 27, 1999 Accepted August 20, 2001

Referee I: D. Rabinovich Referee II: E. J. Valente