Author name:
فرح سعدون جعفر
Supervisor name:
محاسن فيصل الياس
Abstract:
في هذا البحث تم استخدام احدى تطبيقات الكيمياء الخضراء حيث حضرت المعقدات بالطريقة المايكرويفيه حيث تتيح هذه الطريقه ظروف افضل للعمل من حيث تقليل التلوث ,استخدام كمية مذيب اقل, اقل تكلفة, نسبة منتوج عاليه , تفاعل بزمن اقصر وكطريقة عمل ابسط.تم استخدام ليكا | One of green chemistry applications has been used in this work ,where the complexes were prepared by microwave irradiated reactions that availed reduced pollution, free or less solvent conditions, low cost, high yields, shorter reaction times and simplicity in processing. Two of benzothiazole derivatives ligands 2 - benzamid benzothiazole (L1) and 2 - acetamid benzothiazole (L2) were used to synthesize two types of transition metal complexes ; Rh(III), Pd(II), Cd(II), Pt(IV) and Au(III) , the other set of complexes was prepared in presence of a co - ligand 1,10 - phenanthroline(L') or 4,4? - dimethyl - 2,2? - bipyridyl (L") with the metal ions V(IV), Cr(III), Co(II), Ni(II), Cu(II), Zn(II) and Au(III) using microwave and conventional methods to compare the results between them. These ligands and their metal complexes were isolated and characterized in solid state using FT - IR, UV - Vis spectroscopy, flame atomic absorption, elemental analysis C.H.N.S. and magnetic susceptibility measurements as well as melting point and conductivity measurements. According to the results of the above measurements, the following shapes were suggested for the prepared complexes : Complexes of ligand (L1) : Complexes of Rh(III), Pd(II) and Au(III) have a square planar geometry, while Cd(II) complex has a Td geometry and Pt(IV) complex has an Oh geometry.Complexes of mixed ligands (L2 with L'/ L") : All complexes have an Oh geometry except V(IV) complex has a square pyramid and Co(II) complex has a Td geometry. The nature of bonding between the metal ion and the donor atoms of the ligands was demonstrated through the calculation of Racah parameter and other ligand field parameters, which were calculated using suitable Tanabe - Sugano diagrams.The nature of some (L1) complexes in liquid state was studied by following the molar ratio method which gave results approximately identical compared with those obtained from the isolated in the solid state; also, stability constants of the prepared complexes were studied , they were stable in the molar ratio 1 : 1. A theoretical treatment of the ligands and the prepared complexes in gas phase was done using two programs; Hyperchem - 8 and Gaussian program (GaussView Currently Available Versions (5.0.9) along with Gaussian 09 which is the latest in the Gaussian series of programs).Hyper chem. - 8 program used the molecular mechanics and semi - empirical calculation, the heat of formation (?H?f), binding energy (?Eb) dipole moment (µ) for the free ligands and their metal complexes were calculated using ZINDO/1, PM3 and AMBER methods at 298 K. It was found that the complexes were more stable than their ligands; furthermore, the electrostatic potential of free ligands was calculated to investigate the reactive site of the molecules, PM3 was used to evaluate the vibrational spectra of free ligands ,the obtained frequencies agreed well with those values experimentally found; in addition, the calculation helped to assign unambiguously the most diagnostic bands. Electronic spectra measurements for the ligands were calculated theoretically using ZINDO/S method comparing it with the experimental results. It was found that there was a closely relationship between the theory and experimental spectra.Gaussian program semi - empirical (PM3) method which used in order to calculate : the geometry optimization, dipole moment (?),total energy ,electrostatic potential, ELUMO and EHOMO was obtained, evaluate the vibrational spectra of free ligands and these obtained frequencies agreed well with those values experimentally found.Also electronic spectra measurements for the ligands were calculated theoretically by using the job type : Single point energy (SP) along with ZINDO method and also the job type frequency (Freq) used along with CIS method (3 - 21G).
