Preparation and Characterization of some Transition Metal Complexes with OleylXanthate and 1,10- Phenanthrolin

Xanthatecomplexes of the general formula [M{Ag(oleylXant)2}2] (A) and [MM'(oleylXant)4] (B) were M = Copper (II), Nickel II), Cobalt (II) M' = Cadmium(II), Zinc(II). These complexes were reacted with bidentatelewis base (1,10-phenanthroline). The result of this reaction gave the complexes [M(phen)][{Ag(oleylxant)2}2] (I.A) and [M(phen)][M'(oleyl-xant)4] (I.B), which have been prepared and measured by an infrared, magnetic suscetptibility measurements, conductance measurements, electronic spectra and elemental analysis electronic absorption spectra. These data indicate gave the result that the complexes of the type (A & B) are a square planer geometry while the complexes of the type (I.A), (I.B) have an octahedral geometry.

Xanthate mostly refers to a salt with the formula ROCS 2 -M + (R=alkyl; M + = Na + , K + ) (IUPAC, 1997).Zeise is the one who discovered the xanthates for the first time in 1822 (Zeis, 1980), and was used by industry as flotation agents for the thiophilic minerals of the transition metals such as copper, zinc, cobalt, nickel and gold (Han, 1992).They use it as reagents for the separation and quantitative determination of a large number of cations.Xanthate of a few of the transition metals have been prepared in last years to determine their compound and structure (Exarchos et al., 2001).

MATERIAL AND METHOD
The purest chemical materials which are supplying from Fluka and BDH.The instrument Brucker Tensor 27 Co.(400-4000 cm -1 ) FTIR spectrophotometer with KBr disc was used for recording infra red spectra data.The measurements of conductivity using 10 -3 M of the complexes solution in dimethylformamide and conductivity's meter PCM 3 jenway at ambient temperature.The spectrophotometer Shimadzu UV-visible (UV-160)was used for recording electronic spectra data using 10 -3 M of complexes solution in dimethylformamide at room temperature and cells of 1 cm quartz.The contents of metal were estimated by AA670 atomic absorption spectrophotomet, also the recoding data of melting points were carried out with the apparatus of Electrothermal 9300.The measurement of magnetic was recorded at room temperature on the solids using Brucker BM6 instrument by Faraday′s process.

preparing of Potasium Oleyl Xanthate
We added olyel alcohol (63.2 cm 3 , 0.2 mol) to (11.2 g, 0.2 mol) of aqueous KOH solution with continous stirring.An ice bath was used to cool down the mixture.Then, adding with stirring (12.03 cm 3 , 0.20 mol) of CS 2 drop wise for (60 min.) in salted ice bath.The resulted precipitate which was formed have been extracted by (150 ml) diethyl ether, finally, we must filtrated the resulted yellow product, then washed it using diethyl ether as a washing solution, at the end dried it with a vacuum.

Preparation of [M{Ag(oleylXant) 2 } 2 ] Complex (I.A.) M = Co(II), Ni(II), Cu(II)
Silver nitrate that was dissolved in distilled water has been added (0.169 gm, 0.001 mole) to (0.7642 gm, 0.002 mole) olylxant which was dissolved in a mixture of dimethyl formamide (DMF) and distilled water in ratio of (20:80%) then addedto a solution that contains the complex K 2 [Ag(oleylxant) 2 } 2 ] added to the solution (0.005 mole) from salt metal M [0.145 gm) hydrated cobalt nitrate salt and (0.145 gm) hydrated nickel nitrate and (0.124 gm) copper sulphate penta hydrate]which was dissolved in distilled water.The precipitate should be filtered then washed with ether and dried under vacuum.

Preparation [MZn(oleyXant) 4 ] Complex (I.C.)
The zinc chloride has been added (0.001 mole, 0.136 gm) dissolved in a mixture of distilled water and ethanol in a 20:80%ratio of ligand solution (0.004 mole, 1.5289 gm) that dissolved in ethanol (20 ml) that makes the complex [K 2 Zn(oleylxant) 4 ] then metal salts (0.001 mole) of added (0.001 mole) from salt metal M [(0.290 gm) hydrated cobalt nitrate and (0.290 gm) hydrated nickel nitrate and (0.249 gm) copper sulphate] was added to the former mixture filtrate precipitate formal, washed with ether and dry it using vacuum.

EXPERIMENTAL RESULTS AND DISCUSSION
The preparation of xanthate ligand was carried out with the reaction of oleyl alcohol and KOH and CS 2 ; preparation of the complexes was done by the reaction of the AgNO 3 or Cd(NO 3 ) 2 .6H 2 O or ZnCl 2 ,CoCl 2 .6H 2 O , NiCl 2 .6H 2 O and CuCl 2 .6H 2 O directly with xanthate ligand.Conductivity's values in DMF solvent for the complexes (A) and (B) have been ranged (13.8 -24.6 Ω -1 cm 2 mol -1 ), (Table 1) which considered to be standard values for the type of non electrolyte in the solvent used (Varma and Prabhakaran, 1989), while the complexes (I.A), (I.B), range from (51.0-67.5)which were found to be 1:1 electrilyte in dimethyl formamide (Aggarwal, 1985).

Infra Red Studies
The band of infra red's spectra at (1196 cm -1 ) in the ligand spectra which was assigned to υ(C-O). in complexes.This band was shifted to a higher frequency and observed in the range (1215-1268 cm -1 ) and υ(C-S) shifted to lower frequency (1018-1052 cm -1 ) (Serrano et al., 2003).Also, new band of infer red spectra recorded (418-468 cm -1 ), this range is the evidence for the metal's coordination to sulphur υ(M-S) (Rathore et al., 2007), (Table 2).

The Studies of Electronic Spectra
The ligands and their complexes ultra violet-visible spectra in (10 -3 M) in dimethylformamide have been recorded and tabulated as showing in (Table 2) the UV-Vis.The complex spectra of the Co(II) (1, 3, 5) show two absorption bandsat (11407 -11520 cm -1 ) (16197 -1629 cm -1 ) which were assigned to (A 1 g B 1 g) and (A 1 g E'g) respectively.The transitions was in a square planar geometry (Bailar et al., 1975).
The values of magnetic moment for four Cu(II) complexes (13,15,17) are (1.42-1.62B.µ) that correspond to the spin only value irrespective of the stereo chemistry, which suggests a square planer geometry around Cu(II) ion.The values of magnetic moment for hexa coordinated Cu(II) complexes (14, 16, 18) (Table 1) are in the range (1.78 -1.94B.µ).The observed range is similar to other reported values of octahedral Cu(II) complexes (Saha and Gayen, 1983).CONCLUSION A new hetrobimecallic complexes were prepared from some transition metal ions, two series were used in this paper, the first one including Cobalt(II), Nickel(II), Copper(II), while the second one included the non-transiton metal ions which were Zinc(II), Cadmium(II).As well as the ligand which was used named olyelxanthate, all the data were recorded experimentally for the resulted complexes as it assigned in this work, type complexes were hetrobimetallic tetra xanthate which react with 1,10-phenathroline to produce octahedral complexes.