Synthesis and Characterization of Fe ІІ , Co ІІ , Ni ІІ , Cu ІІ and Zn ІІ Complexes With Dithiocarbamate and N-Donor Ligands

New complexes of first series of transition metals with P-amino benzene dithiocarbamate of the general formula [M(PABdtc)2] and [ M(PABdtc)2(L)n] M=Fe( ІІ ),Co( ІІ ),Ni( ІІ ) ,Cu(ІІ) and Zn (ІІ). PABdtc = Paraamino benzene dithiocarbamate ,n=2 when L= Py,ɣ-Pic,iso qunoline ,3,5lutidine n=1when L=1,10-phenanthroline, en, 2, 2bipy.and the type(R)4N[Ni(PABdtc)3] R= methyl, ethyl are prepared. Physico chemical characterization of these complexes was applied using magnetic susceptibility measurements, molar conductance , Infrared and electronic spectra, Metal content measurements, molar conductance indicate complexes of the type [M(PABdtc)2] and [M(PABdtc)2(L)n] are non-electrolyte while complexes of the type (R)4N[Ni(PABdtc)3] are 1:1 electrolyte. Magnetic moment and electronic spectra indicate that the complexes of the type [M(PABdtc)2] are tetrahedral geometry while the complexes of the type [M(PABdtc)2(L)n] and (R)4N[Ni(PABdtc)3] have octahedral geometry.


Introduction
Metal complexes play an essential role in agriculture, pharmacy, medicine and chmical industries [1].Complexes of salicyaldehyde were among the first systems which were studied by infrared spectroscopy [2].Simalarly dithiocarbamate metal complexes are known for their dithiocarbamate metal complexe whic are known for their various applications [3]which include vulcanization accelerators, high pressure lubricants, and active ingredients of fungicides, pecticides and pharmaceutical product.[4,5,6] This kind of compounds has been reported in literature to show detoxicant and immunophavm acological properties such as antibacterial ,antifungal etc [7] ,also they have been reported as group of useful bridging ligands for creating mixed valence poly nuclear system [8].Anextensive search through literature showed that many mixed ligand dithiocarbamate complexes with Schiff base moiety as a part of its coordination ligand have been widely reported [8].

Experimental
All reagents and solvents were of analytical grade and used as supplied from fluka or BDH chemical companies infrared spectra which were recorded on Brucker Tensor 27Co.FTIR spectrophotometer in 400-4000 cm -1 range using KBr discs: and CsI discs in the range 4000-2000 Conductivity measurements were carried out on 10 -3 M solution of the complexes in DMF using conductivity meter PCM3 Jen way at ambient temperature .The electronic spectra were recorded on ashimadzu UV-visible spectrophotometer UV-160 for 10 -3 M solution of complexes in DMF as a solvent at 25 ₒ C using 1cm quartz cell.Metal content was determined using AA670 atomic absorption .Melting point was recorded on an electro chemical 9300 apparatus and uncorrected.The magnetic measurements were carried out of the solids by faradys method using Brucker BM 6 instrument.

Prepation of sodium p-phenylene diamine dithiocarbamate :
The p-phenylene diamine dithiocarbamate ligand(PABdtc) was prepared by literature method [7] by adding (0.1mol,10.81g) of p-phenylene diamine dissolve in 15 cm 3 distilled water to a solution (0.1mol,4.0g) of sodium hydroxide with reflux 30 mint and continuous stirring .The resulting mixture was cooled in ice and (0.1 mol,76g) carbon disulfide was added dropwise with continous stirring .The crude product was extracted by ether, the form precipitate was filtered off , washed with ether and dried.The reaction is shown in figure (1).

Preparation of complexes [M(PABdtc) 2 (L) 2 ]
L= Py,ɣ-Pic, 3,5-lutidine, Isoquinoline In to a solution contining (0.002mol,0.412g) of Na-PABdtc ligand dissolved in 10cm 3 acetone/ water 80/20 was added to (0.001mol)of metal salt and (0.002 mol,0.158g) of pyridine was added .The mixture was continuously stirred for 30 mint .The precipitate formed was filtered and washed with acetone and dried.other complexes of nitrogenous base prepared by the same procedure above.The reaction is shown in figure (3).
The complexes prepared by the same procedure were shown in 2-1 and add (0.001mol,0.1982g) of 1,10-phen.dropwise with continous stirring for 30 mint.The precipitate formed was filtered and washed with acetone and dried.The reaction is showin is figure (4).
To a solution of (0.003mol) of Na-PABdtc dissolved in ethanol was added (0.001mol)of tetramethyl ammonium chloride dissolved in distilled water was added The mixture was stirring (0.001mol of Ni(NO 3 ) 2 .6H 2 O) The precipitate was filtered off and washed with acetone and dried.The reaction is shown in figure (5).

Results and discussion
The new ligand was prepared for the reaction of P-phenylenediamine with sodium hydroxide then reflux 30 mint then added carbon disulfide, the complexes were prepared through direct reaction of the metal salt, FeSO 4 .7H 2 O or Co(NO 3 ) 2 .6H 2 O or Ni(NO 3 ) 2 .6H 2 O or Cu(NO 3 ) 2 .3H 2 O or ZnSO 4 .7H 2 O hydrous with the above ligand in (1:2) molar ratio.The values of conductivity in dimethyl formamide solution of the complexes range from(1.7-16.77)Ω - .cm 2 .mol - which are typical values for non electrolyte type [9]while complexes of the type ( R) 4 N[Ni(PABdtc) 3 ]are 1:1 electrolyte.

Infra-red spectral studies
The important IR band of ligand and its complexes are listed in table ( 2).The stretching frequency of the υ (C=N) band for the dithiocarbamates was intermediate between the stretching frequencies associated with typical single and double bonded carbon and nitrogen atoms [10].The υ (C=N) and υ (C=S) were observed in the ranges of (1500-1550) cm -1 and (900-980)cm -1 .The presence of only one band in the later region reports the bidentate coordination of the dithio ligand [11] .The( N-H) band of dithiocarbamate was observed in the range ( 3319-3455 cm -1 ) IR spectra showed a new band at (420-426)cm -1 the evidence for the coordination of metal to sulfurυ (M-S) , this behaveior may be attributed to the electron releasing of the amines , which forces hig electron density towards the sulfur atoms , the υ (M-N) was observed in the (465-523)cm-1 region [12] In the adduct ,the band corresponding to υ (N-H) of the ethylene diamine (6,14,22,32 and 40) was observed at lower frequency (3211-3270)cm -1 (13) .which indicates that it was shown in coordination with metal ions , as well as the band υ (C=N) ring which was observed as (1479-1500)cm -1 which means the coordination of the donor atoms with the metal ions [14] .

Table ( 1) : Analytical and some physical properties of the prepared cmplexes
*=Degree of disintegration