The Inorganic Chemistry : An Indian Journal B

Author dr Mirjana Dimitrijevi Faculty nature science, department of chemistry Kosovska Mitrovica Republic of Serbia

DISTORSION AND STEREOCHEMISTRY COPPER (II) CHELATE COMLEXES

Copper (II) ion for as dominate complexes with coordination numbers 4,5 and 6, but different to other transition metals. Cu (II) ion characterized by variation in distorsion, which has been established crystalloografically[1]. Ni (II) ion characterized regular octahedral and tetrahedral geometry but Cu (II) complexes extended tetragonal (D4n) or rombic octahedral structure 3,4. tetrahedral geometry Cu (II) ion alwaus recurred some compression along S4 axis simetry D2d picture 1.

Figure 1. Stereochemistry Cu (II) ions in monomolecular complexes, group simetry and bond length, (-) short 1,9-2,1 Ao, (-----) middle 2,1-2,4 Ao, and (--------) long 2,4-3,0 Ao. Square plannar geometry (D2n) is regular for both M (II) ions (M(II) = Ni (II), Cu (II)). Penthcoordinnated complexes Ni (II) ions are regular structures 5, but complexes Cu (II) ions has same regular square - plannar stereochemistry (C4v), but in

many cases reqired elongation in triagonal (C2v) 6 (picture 1) or tetrahedral distorsion. In case trigonal pyramidal stereochemistry Ni (II) ions formed regular structures (D3n) 5. corresponding Cu(II) ions transfer to square pyramidal structures (C2, picture 1). The dominate distorsion Cu (II) ions in relation to regular octahedral (Oh) has extend tetragonal rombic octahedral 1,7 whit four short. Bonds in plane (Rs) and two long axial bonds (Rl) in the cases six equivalentetly liganos (CuL6), the present distorsion (T) 8 are shown by T=Rs/Rl. Complexes with unequivalently ligands (CuL4X2) tetragonality (T) expressed: Rl(x)(corrected)=Rl(x)(find). Rs(l)/Rs(x) For ligandes H2O and NH3 (table 1) tetragonality (T) has been constant (T~0.8) A large numbers is founded of tetragonal octahedral complexes with highest (T) walues (T=0,85-0,95). It caused by presence helate ligands in axial position which stopped elongation on z - axis 9 a,b so we can described as elipsional simetry 10. Table 1 The walues T, Rs and Rl for Cu (II) complexes

Tetragonality T is shown as function separately Rs and Rl walues (fig. 2a)7, or Rl walues in relate to Rs 11. the results shown gradual variability sterechemistri Cu (II) ions from regular octahedral over extend tetragonal octahedral till square-plannar geometry without two axial ligands

Fig.. 2

a) tetragonality T shown and relate Rs and Rl values b) the values Rl shown in relate Rs

Penta and hexacoordinated complexes Cu (II) ion are equal presented. Regular squared pyramidal geometry vith five equivalent or unequivalen ligand are presented in small cases. 1,12,13. in this structures four bonds are plannar (CuLn, n=1,2,3,4) and normal length (~2,0) for 0, N ligands, and bond (CuL5) are longiest for 0,2-0,5. In this structurec Cu (II) ions is moved to fifth ligand (CuL5) length (=0,1-0,5) with inverse corelation on length CuL5 bond and caused a both trans-ligand in aplane are never linear with arrange angles 160-170 The regular trigonal-bipiramidal geometry is limiting only to a few Cu(II) complexes. 1,14 a large numbers pentacoordinated Cu(II) complexes are distored structures 14 regular square pyramidal and triagonal bipiramidal geometries. The change of the bond length in this complexes are defined tetragonality (T5) as ration four length in plane Cu-l and longiest axial bond. The distorsion angles of this complexes are described by ration 1,15 defined:

And represented ppocent triagonals distorsion in square pyramidal stereochemistry for pentacoordinated Cu(II)complexes the tetragonality values (T5) are represented on the figure 3b, by a large numbers structure informationes. The values T5 are in the range 0,9-0,96 and small large then T6 values. Tetragonality are grown up by increase angle diference (fig. 3b).

Fig. 3

a) dependence Cu-L (5) bond length in ration b) tetragonality T5 dependence from angles difference

In the table 2 are shown structural parameters, asimetry tetragonal bonds and tetragonality (T) for complex: [Cu (H2 edta) (H2 O)][9a] (A), [Mn (H2O)4] [Cu (edta)] 2H2O[16] (B), trans (O5) Mg[Cu (SS-edds)] 7H2O[17] (C), trans (O6) [Cu (H2 1,3-pddadp)] 1.5 H2O[18] (D), trans (O5) Na2 [Cu (1,3-pddadp)] NaNO3 2H2O[19] (E). The complexes (A) are represented ACID complex with pentadentate edta ligand, until B,C,D,E are hexadentate and mostly of them has simetry extend rombie octahedral. Tetragonality complexes (A) is counted by comparison Cu-N bond, and for the rest by comparison Cu-O bond. These complexes has asimetry coplanar bondes, so expressed for structures A,B and C with distorsion square-piramidal stereochemistry. The greates asimetry tetragonal bond (=0,242) is appered in complex C with squarepiramidal stereochemistry. The complex C contain optical ligand SS-edds who favorized trans (O5) isomere () absolute configuration. The presence two six-membered rings in G-plane complexes C16 give possibility the elongation on z-axis then B complexes hexadentate edtha-ligand (tab.2). The individual tetragonality (T) are discussed and showed theire dependence by structures and distorsion complexes. The Cu (II) complexes with H2 edta (A)[9a] and edta (B)[16] has much more T values then it for tetragonal complexes (rombic or regular octahedral stereochemistry) T=(0,80,02)[1,7]. Tetragonal elongation complexes (A) and (B) are limited by presence multidentate edta ligand, wich formed only five-membered rings in axial position. The complexes (D)[18] and with 1,3- pddadp ligand (trans (O6)-configuration) has stereochemistry different by other complexes shown in table 2.

Table 2 Structure parameters hexacoordinated Cu(II) complexes with edta-type ligands Complexes Bond length () Coplanar Tetragonal Asimetry in tetragonal bond () T Lit

9a

16

18

19

Ligand edta act pentadentate ligand, other shown complexes are hexadentate figure More expressive tetragonal elongation on z-axis permitted by two -alaninate rings (R), but theire tetragonality (T) is not much different for expecting tetragonal octahedral complexes with monodentate ligands (0,80)[1,7]. Hexadentate complexes D with protonized (H2 1,3-pddadp) ligand content for unequally rings (two glicinato G and two -alaninator). C2-molecular simetry and extend rombic octahedral stereochemistry. The most simetrical system is complex (E)[19] from another complexes an his tetragonality (T=0,799) expendid for regular tetragonal complexes (0,80). This complexes has two pair (two glycinato G and two -alaninator) rings in total equally, C2-molecular simetry, acting an example of complexes with regular extend tetragonal octahedral stereochemistry.

REFERENCES [1] B. J. Hathaway, in G. Wilkinson, R. D. Gillard and J. A. Mc. Cleverty Comrehensive Coordination Chemistry 5 (1987), Chapt. 53. [2] A. F. Wells, Structural Inorganic Chemistry, 5th edn, Clarendon, Oxford, 1964 [3] B. J. Hathaway and D. E. Billing, Coord. Chem. Rev., 5, (1970) 143, [4] B. J. Hathaway, Essey Chem., 2, (1971) 61, [5] L. Sacconi, Transition Met. Chem., 4, (1986), 199, [6] B. J. Hathaway, Structure Bonding (Berlin), 57, (1984) 55, [7] B. J. Hathaway and P. G. Hotgson, J. Inorg. Nucl. Chem., 35, (1973) 4071, [8] A. A. G. Tomilson, B. J. Hathaway, D. E. Billing and P. Nichols, J. Chem. Soc. A, (1969) 1723 [9] (a) F. S. Stephens, J. Chem. Soc. A, (1969) 1723, (b) Tbid 2233 (1969). [10] H. A. Jahn and E. Teller, Proc. Roy. Soc., A 161, (1937) 220; H. A. Jahn, ibid, A 164, 117, (1938) [11] J. Gao, R. Roa, E. Jona, M. Kabeova, L. Macakova, J. ima, P. Pelikan and F. Valach, Coord. Chem. Rev., 43, (1982) 87, [12] M. Duggan, N. Ray, B. J. Hathaway, G. Tomilson, P. Brint and K. Pelin, J. Chem. Soc., Dalton trans, 1342, (1980) [13] F. Massi, Acta Cristallogr., 8, 137, (1955); B. Morosin, Acta Cristallogr., B 25, 19, (1969) [14] M. Mori, Y. Saito and T. Watanabe, Bulb. Chem. Soc. Jpn., 34, 295, (1961); I. Bernal, J. D. Corp, E. O. Schlemper and M. S. Hussain, Polyhedron, 1, 365, (1982) [15] A. W. Addison, T. Nageswara Rao, J. Reedijk, J. Van Rijn and G. C. Verschoor, J. Chem. Soc. Dalton trans, 1349, (1984) [16] X. Solans, M. Font-Altaba, J. Oliva and J. Herrera, Acta Crystallogr. Sect. C 39, (1983) 435, [17] J. Soldanova, F. Pavelik and J. Mayer, Acta Crystallogr. B 37, (1981) , 921 [18] V. Prelesnik, D. D. Radanovi, D. T. urevi, J. D. Tomi, D. J. Radanovi and D. S. Veselinovi, Polyhedron, 15, (1996) 3761, [19] D. J. Radanovi, B. V. Prelesnik, D. D. Radanovi, Z. D. Matovi and B. E. Douglas, Inorg. Chem. Acta., 262, 203, (1997)