TY - JOUR ID - TI - Synthesis, Characterization, Theoretical studies and Biological activities of bimetallic Complexes of new Schiff base thiadiazole derivative with some trivalent metal ions AU - Rehab A.M. Al-Hasani PY - 2009 VL - 7 IS - 3 SP - 64 EP - 79 JO - journal of kerbala university مجلة جامعة كربلاء SN - 18130410 AB - Tetrachloro [5-(5---phenyl-3---N-ethyl-2---thiazolene)imino-3-N-ethyl-2-thion-1,3,4- thiadiazole].tetanium(IV), of a new Schiff base{TiL}derived from[ tetra chloro (5- amino-3-N- ethyl – 2 -thione-1, 3 ,4 – thiadiazole).tetanium(IV)] and(3-N-ethyl- 2-one –1 ,3,4-thiadiazaole) have been prepared.The product was characterized by by (FT-IR) ,(UV-Vis) Spectroscopy and elemental analysis (C.H.N.S) . {TiL}has been used as a chelating ligand to prepare a number of metal complexes with[Cr(Ш), Fe(Ш) , Ru(Ш), Rh(Ш) and Au(Ш)] . The prepared complexes were isolated and characterized by using (FT-IR) and (UV-Vis) spectroscopy, elemental analysis (C.H.N.S), Flame atomic absorption technique, in addition to magnetic susceptibility and conductivity measurements. Molar ratio method measurement in solution gave comparable results with those obtained from solid state studies. The work also include a theoretical treatment of the formed complex in the gas phase, this was done using the Hyperchem-6 program for the Molecular mechanics and Semi-empirical calculations. The heat of formation (∆Hf°) , binding energy (∆EB ) and bond length (∆EL) for [ASN] , [TiA]and {TiL} ligand and their metal complexes were calculated by (PM3 and AMBER) methods at 298 K°. Furthermore the electrostatic potential of the free ligand{TiL} was calculated to investigate the reactive sites of the molecules .PM3 were used to evaluate the vibrational spectra and electronic spectra of the ligand{TiL} and it's metal complexes(A1-A5( then compare the theoretically calculated wave numbers with the experimental values by using the [ASN] and [TiA]as authentic compounds .The theoretically obtained frequencies agreed with those found experimentally, in addition the calculation helped to assign unambiguously the most diagnostic bands.

Abstract: Tetrachloro [5-(5---phenyl-3---N-ethyl-2---thiazolene)imino-3-N-ethyl-2-thion-1,3,4- thiadiazole].tetanium(IV), of a new Schiff base{TiL}derived from[ tetra chloro (5- amino-3-N- ethyl – 2 -thione-1, 3 ,4 – thiadiazole).tetanium(IV)] and(3-N-ethyl- 2-one –1 ,3,4-thiadiazaole) have been prepared.The product was characterized by by (FT-IR) ,(UV-Vis) Spectroscopy and elemental analysis (C.H.N.S) . {TiL}has been used as a chelating ligand to prepare a number of metal complexes with[Cr(Ш), Fe(Ш) , Ru(Ш), Rh(Ш) and Au(Ш)] . The prepared complexes were isolated and characterized by using (FT-IR) and (UV-Vis) spectroscopy, elemental analysis (C.H.N.S), Flame atomic absorption technique, in addition to magnetic susceptibility and conductivity measurements. Molar ratio method measurement in solution gave comparable results with those obtained from solid state studies. The work also include a theoretical treatment of the formed complex in the gas phase, this was done using the Hyperchem-6 program for the Molecular mechanics and Semi-empirical calculations. The heat of formation (∆Hf°) , binding energy (∆EB ) and bond length (∆EL) for [ASN] , [TiA]and {TiL} ligand and their metal complexes were calculated by (PM3 and AMBER) methods at 298 K°. Furthermore the electrostatic potential of the free ligand{TiL} was calculated to investigate the reactive sites of the molecules .PM3 were used to evaluate the vibrational spectra and electronic spectra of the ligand{TiL} and it's metal complexes(A1-A5( then compare the theoretically calculated wave numbers with the experimental values by using the [ASN] and [TiA]as authentic compounds .The theoretically obtained frequencies agreed with those found experimentally, in addition the calculation helped to assign unambiguously the most diagnostic bands. The antibacterial activity for [ASN], [TiA] and free ligand {TiL} and their metal complexes(A1-A5( were studied against two selected micro - organisms [(Pseudonomous aerugionosa) as gram negative] and[(Bacillus Subtilis) as gram positive]. The minimal inhibitory concentrations (MIC) have been also studied to determine the low concentration for inhibition. The antibiotic (Ampicillin) has been chosen to compare their activity with those of the new compounds. Further more the antifungal activity against two micro-organism (Penicillum Spp.) and (Aspergillus flavus) were studied for all compounds. The results showed great enhancement of activity of the complexes relative to that of their respective [ASN], [TiA] and free ligand {TiL}.This was attributed top the synergetic effect between the metal ion and the ligand, in addition to the differences in the structural varieties.الخلاصة: يتضمن هذا البحث تحضير مشتق لقاعدة شف الجديدة: Tetra chloro [5-(5-- -phenyl-3-- -N-ethyl-2-- -thiazolene)imino-3-N-ethyl-2-thion-1,3,4- thiadiazole].tetanium(IV).{TiL} من عملية تكاثف ) . tetanium (IV) ] [ tetra chloro ( 5- amino - 3 - N- ethyl – 2 –thione – 1 , 3 ,4 - thiadiazole مع (5-phenyl-3-N-ethyl- 2-one – 1,3,4-thiadiazaole).جرى تشخيص {TiL} بطرائق تحليل طيف الاشعة تحت الحمراء (FT-IR) وطيف الاشعة فوق البنفسجية-المرئية والتحليل الدقيق للعناصر C.H.N.S)) .تم استخدم قاعدة شف {TiL}كليكاند في تحضير معقدات الايونات الفلزية الثلاثية (الكروم و الحديد و الروثينيوم و الروديوم و الذهب ).تم عزل المعقدات الجديدة وتشخيصها باستخدام طيف الاشعة تحت الحمراء وطيف الاشعة فوق البنفسجية-المرئية وتقنية C.H.N.S)) وتقنية الامتصاص الذري اللهبي للعناصر اضافة الى قياسات الحساسية المغناطيسية والتوصيلية الكهربائية . تم قياس النسبة المولية للفلز مع{TiL} في المحلول وقد اعطت هذه الدراسة نتائجا مطابقة مع تلك التي تم الحصول عليها في الحالة الصلبة. تضمن العمل ايضا معالجة تكوين المعقدات نظريا في الطور الغازي ،باستخدام برنامج (6-Hyperchem) وبتطبيق الميكانيك الجزيئي والشبه التجريبي في الحساب وباستخدام الدوال PM3) و (AMBER لحساب حرارة تكوين (∆Hf) وطاقة التاصر (∆Eb) و أطوال الأواصر (∆EL) وبدرجة حرارة 298 كلفن للمركبات [ASN]و [TiA]و لليكاند {TiL}و معقداته المحضرة , كذلك تم حساب الجهد الكهروستاتيكي لليكاند{TiL} لبيان المواقع الفعالة ضمن الجزيئة .جرى كذلك حساب التردد الاهتزازي والاطياف الالكترونية نظريا وبإستخدام الدالة PM3 لليكاند{TiL} )ومقارنتها مع القيم المقاسة عمليا بإستخدام ASN]و [TiAكمركبات قياسية) ومعقداتها ( (A1-A5وجد بان هنالك توافقا كبيرا بين القيم العملية والمحسوبة نظريا مع إمكانية تشخيص الحزم بشكل أدق. تمَّ تقويم الفعالية المضادة للبكتريا للمركبات ASN]و [TiAو لليكاند{TiL} ومعقداته وأُختير نوعان من البكتريا Pseudonomous aerugionosa ) ) سالبة الصبغة و (Bacillus Subtilis) موجبة الصبغة لهذا الغرض ودراسة أقل تركيز يحدث عنده التثبيط (MIC). تمت مقارنة فعالية المركبات المحضرة مع المضاد الحيوي (Ampicillin). كما تم اجراء التقويم الحيوي للمركبات ASN]و [TiAو لليكاند{TiL} ومعقداته ضد نوعين من الفطريات Penicillum Spp.) و (Aspergillus flavus flavus وقد أظهرت نتائج التقويم زيادة كبيرة في فعالية المعقدات المحضرة منها.تم تفسير الفعالية المضادة للبكتريا و الفطريات إلى التأثير المتداوب للفعالية بين الفلز و الليكاند فضلآ عن الإختلاف في تراكيب المركبات المحضرة ER -