Elif Ece İLTER, Zeynel KILIÇ, Nuran ASMAFİLİZ

$O_2N_2$- ve $O_2N_3$-donör atomlu makrohalkaların Ni (II) Co(II) ve Pd(II) komplekslerinin sentezi ve yapılarının incelenmesi

$O_2N_2$- ve $O_2N_3$-donör atomlu makrohalkalı bileşiklerin Ni(II), Co(II) ve Pd(II) ile olan etkileşimleri incelenmiş ve dört adet yeni koordinasyon bileşiği ($L^1a, L^2a, L^2b, L^3a$ ve $L^4a$) sentezlenmiştir. 15- ve 16-üyeli makrohalkalı komplekslerde ($L^1a$ ve $L^2a$), eterik oksijenler Ni(II) ve Co(II) iyonlarıyla koordinasyona girerken, 17- ve 19-üyeli olanlarda eterik oksijenlerle Pd(II) iyonları arasında bir koordinasyon bulunmamaktadır. Elde edilen komplekslerin yapıları, FTIR, ES-MS, TGA, DSC, $^1H$- ve $^{13}C$-NMR, elementel analiz ve magnetik duyarlılık ölçümleri teknikleri ile aydınlatılmıştır. Ni(II) ve Co(II) komplekslerinin ($L^1a$ ve $L^2a$) oktahedral geometride, Pd(II) komplekslerinin ($L^2b, L^3a$ ve $L^4a$) ise kare düzlem geometride oldukları bulunmuştur. TGA ve DSC verilerine göre, $L^4a$ kompleksinde Pd(II) iyonu ile bağ yapmayan iki, bağ yapan bir su molekülü olduğu, diğer komplekslerde ise su bulunmadığı anlaşılmıştır.

Synthesis and structural investigation of Ni(II), Co(II) and Pd(II) complexes of$O_2N_2$- and $O_2N_3$- donor type macrocycles

The interactions of $O_2N_2$- and $O_2N_3$-donor type macrocycles with Ni(II), Co(II) and Pd(II) have been investigated and four new complexes ($L^1a, L^2a, L^2b, L^3a$ and $L^4a$)have been prepared. In 15- and 16-membered macrocyclic complexes ($L^1a$ and $L^2a$), the etheric oxygens are coordinated to Ni(II) and Co(II) ions, while in 17- and 19-membered macrocyclic complexes the etheric oxygens do not coordinate to Pd(II) ions. Comparative FTIR, ES-MS, TGA, DSC, $^1H$- ve $^{13}C$-NMR, elemental analyses and magnetic measurements have been used to elucidatethe nature of the species formed. The Ni(II) and Co(II) complexes ($L^1a$ and $L^2a$) were found to be in octahedral geometry, while the Pd(II) complexes ($L^2b, L^3a$ and $L^4a$) have square planar structures. $L^4a$ contains three water molecules, in which one water molecule is coordinated to Pd(II) ion as a ligand, while the other complexes do not contain any water molecule as proven by TGA and DSC data.

PDF

___

1. G. W. Gokel, W. M. Leevy, M. E. Weber, (2004). Crown Ethers: Sensors for Ions and Molecular Scaffolds Materials and Biological Models, Chem. Rev., 104, 2723.
2. Y. Jin, H. Yoon, J. Seo, J. Lee, S. Moon, J. Kim, S. W. Han, K. Park, L. F. Lindoy, S. S. Lee, (2005). Cadmium(II) and mercury(II) complexes of an NO2S2-donor macrocycle and its ditopic xylyl-bridged analogue, J. Chem. Soc. Dalton Trans., 788.
3. V. Gasperov, S. G. Galbraith, L. F. Lindoy, B. R. Rumbel, B. W. Skelton, P. A. Tasker, A. H. White, (2005). A study of the complexation and extraction of Cu(II) sulfate and Ni(II) sulfate by N3O2-donor macrocycles, J. Chem. Soc. Dalton Trans., 139.
4. J. R. Price, M. F. Melnikova, R. R. Fenton, K. Gloe, L. F. Lindoy, T. Rambusch, B. W. Skelton, P.Turner, A. H. White, K. Wichmann, (2004). Macrocyclic ligand design. Structure–function relationships involving the interaction of pyridinyl-containing, oxygen nitrogen donor macrocycles with selected transition and post transition metal ions on progressive N-benzylation of their secondary amines, J. Chem. Soc. Dalton Trans., 3715.
5. C. J. Pedersen, (1967). Cyclic Polyethers and Their Complexes with Metal Salts, J. Am. Chem. Soc., 89, 10, 2179.
6. Z. Hayvalı, M.Hayvalı, Z. Kılıç, T. Hökelek, E. Weber, (2003). New Benzo-15-Crown-5 Ethers Featuring Salicylic Schiff Base Substitutions – Synthesis, Complexes and Structural Study, J. Incl. Phenom. Macromol. Chem. 45, 285.
7. J. Kim, T. Ahn, M. Lee, A. J. Leong, L. F. Lindoy, B. R. Rumbel, B. W. Skelton, T. Strixner, G. Wei, A. H. White, (2002). Metal ion recognition. The interaction of cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II), silver(I) and lead(II) with N-benzylated macrocycles incorporating O2N2-, O3N2- and O2N3-donor sets, J. Chem. Soc. Dalton Trans., 3993.
8. J. Kim, A. J. Leong, L. F. Lindoy, J. Kim, J. Nachbaur, A. Nezhadali, G. Rounaghi, G. Wei, (2000). Metal ion recognition. The interaction of cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II), silver(I) and lead(II) with N-benzylated macrocycles incorporating O2N2-, O3N2- and O2N3-donor sets, J. Chem. Soc. Dalton Trans., 3453.
9. K. R. Adam, D. S. Baldwin, L. F. Lindoy, G. V. Meehan, I. M. Vasilescu, G. Wei, (2003). Metal-ion recognition. Modeling the stability constants of some mixed-donor macrocyclic metal ion complexes—a simple model, Inorg. Chim. Acta, 352, 46.
10. L. F. Lindoy, (1997). Tailoring macrocycles for metal ion binding, Pure Appl. Chem. 69, 2179.
11. J. D. Chartres, A. M. Groth, L. F. Lindoy, M.P. Lowe, G. V. Mechan, (2000). New heteroditopic, linked macrocyclic systems derived from selectively protected N2S2-, N3O2- and N4-donor macrocycles, J. Chem. Soc. Perkin Trans. 1, 3444. ,
12. T. Hökelek, N. Akduran, E. E. Kaya, Z. Kılıç, (2000). Crystal Structure of 2,6-dioxa-14,18-diaza-tricyclo-[18.4.0.$0^{7,12}$]- tetracosa -7,9,11,20,22,24(1)-hexaene, Anal. Sci., 997.
13. T. Hökelek, E. E. Kaya, Z. Kılıç, (2001). 2,7- dioxa - 15,19 – diazatricyclo-[19,4,0,$0^{8,13}$]-pentacosa-8,10,12,21,23,25(1)-hexaene Acta Cryst., E57, o309.
14. T. Hökelek, E. E. Kaya, Z. Kılıç, (2004). 1,14-Dioxa-5,10-diaza-2,3:12,13 dibenzocycloocta-deca-2,12-dienemonohydrate, Acta Cryst., C60, o278.
15. T. Hökelek, E. E. Ilter, Z. Kılıç, (2004). Crystal structure of 3,4:11,12-dibenzo-5, 10-diazacyclohepta- deca-1,14-diammonium nitrate, Anal. Sci., 20, x69.
16. T. Hökelek, E. E. Ilter, N. Asmafiliz, Z. Kılıç, (2004). Cryst triazatricyclo-[21.4.0.$0^{8,10}$]-heptacosa-8, 10, 12, 23,25,al structure of 2, 7-dioxa-15, 18, 21 -27(1)-hexaene, Anal.Sci., 163.
17. S. Bilge, Z. Kılıç, T. Hökelek, B. Erdoğan, (2004) Complexes of Ni(II) and Pd(II) Ions with 15- and 17- Membered Macrocycles Containing O2N2- and -O2N3- Donors and Crystal Structures of Ni (II) and Pd (II) Complexes of 2,5-Dioxa-13, 16, 19- triaza -tricyclo-[19.4.0.06,11]-pentacosa-6,8,10,21,23,25(1)-hexaene, J.Mol.Struct., 691.
18. P. G. Grimsley, L. F. Lindoy, H. C. Lip, R. J. Smith, J. T. Baker, (1977). Synthesis of 15- and 16-Membered Crown Compounds Containing New 14- Oxygen and Nitrogen Heteroatoms, Aust. J. Chem.30, 2095.
19. A. Ekstrom, L. F. Lindoy, H. C Kinetics and mechanism of formation of nickel (II). Lip, R. J. Smith, H. J. Goodwin, M. McPartlin, P. A.Tasker, (1979). complexes of nitrogen – oxygen donor macroc ligands in methanol, and the X-ray structure deter yclic mination of one 9,10,11,17,18-octahydro-5H-dibenzo[e,n][1,4]dioxa-of the products, dichloro-( 6, 7, 8, 9,1[8,12] - diazacyclopentadecine) – nickel(II), J. Chem.0,11,17,18-octahydro-5H-dibenzo[e,n][1,4]dioxa- Soc. Dalton Trans., 1027.
20. A. Ekstrom, L. F. Lindoy, R. J. Smith, (1980). Kinetics of Dissociation of Nickel (II)Cornplexes of a Series of 0 Donor Macrocycles in Acid, Inorg. Chem. 19, 724.
21. K. R. Adam, M. Antolovich, P. A. Duckworth, A. J. Leong, L. F. Lindoy, M. McPartlin, P. A.Tasker, (1993). Ligand design and metal-ion recognition. The interaction of copper (II) with a range of 16- to 19- membered macrocycles incorporating oxygen, nitrogen and sulfur donor atoms, J. Chem. Soc. Dalton Trans., 1013.
22. T.Hökelek, O.Büyükgüngör, E.E.İlter, Z.Kılıç, (2005).Crystal Structure of [2,6-Dioxa-14,18-diaza-tricyclo-[18.4.0.$0^{7,12}$]-tetracosa-7, 9, 11, 20, 22, 24(1)-hexaenediacetato]-palladium(II), Anal. Sci., (baskıda).