Chemistry - 311 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 Preparation Of Ferrocene Derivatives Of Niobium IV A.W.M. Abdulla Department of Chemistry,College of Education -Ibn Al.Haetham, University of Baghdad Received in : 26 August 2012 Accepted in : 20 November 2012 Abstract This study included the preparation of the dihalogens -1,3 metalla-2[3] ferrocenophanes like Cp2NbS2Fc,(tBuCp)2NbS2Fc,Cp2NbSe2Fc and (tBuCp)2NbSe2Fe where (Fc=ferrocence) These complexes has been prepared from the reaction of (R)2 NbCl2 with FCLiM2 , where(R=Cp,tBuCp) (M = S,Se) under refluxing in toluene,the reaction was carried under Argon atmosphere . These complexes were characterized by elemental microanalysis ,Masse spectra scopy, nuclear magnetic resonance (1HNMR) and melting points . Key words: Ferrocene , Niobium ,Selenium , Sulfur ,Inert Atmosphere Organometalic complexes Introduction The early studies consist the reaction of the compounds as follows 2MeCpli +NbCl4 (MeCp)2 NbCl2 [1] And products like (MeCp)2NbOCl ,(iPrCp)2 NbOCl. CpNbCl4 etc, by other side ferrocene has much derivatives with transition metals like Zr,Ti,Hf,Co,Mn and many others [2] To understand the Niobium compounds properties we must know something about it physical properties like density mpc bpc covalent diameter as follows 8.57 2470 4927 0.134 In base temperature Niobium becomes super conductor, Niobium halogene derivatives as Niobium tetra chloride which react with ferrocene to produce the complexes of our work . Ferrocene has two iso energetic [3] conformations eclipsed and staggered [3][4]. but the x-ray and electron diffraction indicate an eclipsed conformation , the rotation barrier about the iron- Cp ring axis is very weak (2-5kcal.mole), thus the rotation about that axes is,so in fluid solution we find only one 1,1disubstituted isomer [5,6] , because the free rotation makes all position on the first ring equivalent to the second ring The ferrocene molecular orbital diagram shows various metal ring interactions , (Cp Fe) ,λ(Cp Fe) and (Cp Fe) so the reaction of dichaleogene with (Ti,Zr,Hf) underegoes all the important reactions of the early works [7,8]. But reaction between niobium derivatives and ferrocene derivative are not found , so our work focus to prepare new complexes of ferrocene Niobium derivatives. Results and dissuasion To obtain these complexes we follow the procedure bellow (RCp)2NbCl2 + Fc(MH)2 (RCp)2NbM2Fc Cp2NbCl2 + Fc(MH)2 Cp2NbM2Fc R = +Bu Fc = Ferrocen Cp = C5H5 M = S,Se Chemistry - 312 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 NMR Study In CdCl3 we get a clear signals which assist groups of massive For the ferrocene between two to four ,there is a variety of chemical displacement without any change of the morphology of the NMR spectrum [10] , the comparison between the spectrums of (S) and (Se) complexes leads to the fact that there is a displacement toward the faible field of the forrocenic massives [11] of (S) complexes than that of(Se) . The effect of the free electron pair [12] of (S) or (Se) toward the other (H) atom of C5H5 ring neighbor at the proton , we constat that the ring torsion is due to the steric [13,14] Experiments All the complexes performed under Inert gas preparation of A. Cp2NbS2Fc :-To a solution of FcS2 Li Tmeda (0.7)gm(1.8)m mol in (20) ml of toluene /THF (2/1) , a solution of Cp2NbCl2 (0.5) gm (1.7) m mol in (20)ml of toluene was added , the mixture was refluxed for (30) minutes with stringing an orange crystal obtained (0.55)gm yield (60%) mp 260 dec B. Cp2NbSe2Fc :-To a solution of FcSeH2 A (0.42)gm (1.2)ml in (30ml) of (n) toluene a solution of Cp2NBCl2 (0.34)gm (1.18)m mol in (20) ml of toluene was added , the maximum was refluxed for (2) hours with stirring , an orange crystals obtained (0.42)gm (61%) yield mp mp260 C C. (tBuCp)2NbS2Fc:- To a solution of (0.4) gm (01.1)m mol of (tBuCp)2NbCl2 and (0.3) gm (1.1) m mol of FcS2H2 was added then o.56 ml of Net3 in 50 ml of toluene , the mixture was stirred at 70 C for 3 hour , the product was isolated by chromatography , after recrystallization in hexane, we obtained red crystals (0.3)gm 18yeild F 260 D. (tB4Cp)2NbSe2Fc :-To a solution of (0.5)gm (1.2)m mol of (tB4Cp)2NbCl2 and (0.4)gm (1.1)m mol of FcSeH2 In 50 ml toluene/THF (2/I)then o.65 ml of Net3 was added the mixture stirred at 88 C for 3 hours , the product was isolated by chromatography after rercystalisation in hexane weobtained orange crystals f 260 C 56% yield 50% (0.5)gm (0.7) m mol Instruments: mpc by electro thermal digital mp apparatus TLC: glass plats coated with merckgelC.F.250 silica gel NMR Joel fx(100) of Fourier trans former Chromatography kiesel gel type 3300 (70 ev at 200C) Analysis CNRS France Reference 1- Davison, A. and smart, C. (1979) metalchem,174-322 "symmetrically distributed ferrocenes IV.the preparation and spectral studies of some (3) ferrocenophanes" J.Organ,174:321-334 2- Osborne, G.; G.A.R.E(1981) Holand Org. metal chem. 205-395 "synthetic and structural studies on some [3] ferro cerophanes.205issue(3): 3- Osborne,G. (1984) Organometal chem.29-226 "synthetic and structural studies on some 1,3di Seiena –[3] ferrocenophanes of carbon,silicon and tin ". 4- Wilkinson ,G.(1975) J. Organometalchem 100-273 "the Iron sandwich ". Chemistry - 313 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 5- Gautheron and Taninturier ,G. (1984) .J.Organometal 34-262 "conformation de metalla diselena ferrocenophanes " . 6- Hiller ,S.A. ; Tremaine, J.F. (1959) Di cyelopenta dienyl iron wiley , newyork 7- Abdulwahid, A. (1985) Synthesis et Etude physic chimique de complexes metallocenique (7). 8- Sato ,M. and Yoshi ،T. (1974) Organometal chem..67-399 "selenium and fellurim derivatives of di -ᴨ-cyclo penta dienyl –titanium (IV) and Zirconium (IV) 9- Francis ،A. Carey. (2006) 6th ed, Mc Graw –Hill,Newyork Organic chemistry P557. 10- Ray,P.Q.Rrewster (2007) Organ metallic compounds 11- Cardorell and François (2008) Natural handbook Springer ,London ,Newyork. 12- Crabitree, R.H. (2005) –the Organometallic chemistry of the Transition metals ,Wiley ,Newyork 3rd edd. 13- Yamamoto, A. (mgo) –Organotransition metal chemistry ,Wiley ,Newyork 14- Elshenbroich ,Ch.; Salzer, A. (2006) Organometallics,VCH,Weinheim ,4th ed. Table(1): 1HNMR spectral data for ligands and complexe (chemical shift ) δ in p.p.m C5H5 Cp Complex 5.2(1) 4.5(1) 4.0(2) 5.9(5) Cp2NbS2fc 4.94(1) 4.38(1) 4.31(1) 4.1(1) 5.92(5) Cp2NbSe2fc Cp + C5H4 tBu Complex 576(2) 5.6(1) 5.3 (1) 5.4 (1) 4(1) 1.15(9) 6.42(1) (tBuCp)2NbSe2fe 4.98(1) 4.1(1) 4.0(1) 1.13(9) 5.62(1) 5.01(1) (tBaCp)2NbSe2fe Table (2): physical properties Yield weight of Fc M2Li weight of Nb chloride color mp Compound 60% 0.74 0.52gm Orange 260> Cp2 NbSe2Fc 61% 0.42 0.42gm Orange 260> Cp2NbSe2Fc 48% 0.54 0.7gm Red 260> (tBuCp)2Cp2NbSe2Fc 50% 0.41gm 0.37gm Orange 260> (tBuCp)2Cp2NbSe2Fc Table (3): masse spectral data for the complexes 470(m+) 450(C2H4FeS+) 253(m+) (CpNbSCp)+ Cp2NbSe2Fc 566(m+) 314 (C10H8Fe Se)+ 222(CpH10Nb)+ 184 (C10H8Fe)+ Cp2NbSe2Fc 582 (m+)561(m-tB4Cp)+ (tB4Cp)2NbSe2Fc (678(m+),266(C10H8FeSe) (tBuCp)2NbSe2Fc Chemistry - 314 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 Table (4) :Analytical and physical data for ligands and complexes Calc C43% 4.29 Nb 17 found C 42.55% H3.01Nb 16.8 C2OH18FeFe2Nb Cp2NbSe2Fc Calc C 49.18% H5.94 found C 49.76 % H4.91 C2OH34FeSe2Nb (tBuCp2) NbSe2Fc Calc C 50% H3.8 Nb 1.97 found C 50.8 H3.9 Nb=19.72 C2OH18FeS2Nb (tBuCp)2Nb Se2Fc Table (5) :The solubility of prepared complexes ether hexane THF toluene C2H5OH CH3OH water Cp2NbS2Fc - - + ÷ + + ÷ Cp2NbS2Fc - - + ÷ + + ÷ (tBuCp)2NbS2Fc - - + ÷ ÷ ÷ - (tBuCp)2NbSe2Fe - ÷ + ÷ + ÷ - (tBuCp)2NbSe2Fe Soluble (+) Insoluble (-) Sparingly (÷) Chemicals used in this work and their suppliers NO material Company Purity % 1-Ferrocene 2- TMEDA 3- bUli 4-Cp2NbCl2 5-Toluene 6- THF 7- (tBuCp)2NbCl2 8-Hexane 9- Sulfur 10- Selenium Fc (ScH)2 Merck B.D.H B.D.H Riedel-Ochean Fluka Fluka Merck Merck B.D.H B.D.H Merck 99 99 99 99 99 99 99 99 99 99 99 Chemistry - 315 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 IVتحضير مشتقات الفيروسين للنيوبيوم عبد الواحد محجوب عبد هللا بغداد ةجامع،ابن الهيثم - كلية التربيةقسم الكيمياء، 2012تشرين الثاني 20قبل البحث في : 2012آب 26استلم البحث في : الخالصة فيروسينوفان مثل [3]2ميتاال 3و1ائي كلورو تضمن البحث تحضير معقدات ثن Cp2NbS2Fc,(tBuCp)2 NbS2Fc , Cp2NbSeFc(tBuCp)2NbSe2Fc (Fc هو الفيروسين) تم الحصول على هذه المعقدات من مفاعلة معقدات كلوريدات النيوبيوم مع معقد ثنائي ليثيوم الفيروسين لعنصري وجود التولوين كوسطاً للتفاعل مع اضافة ثنائي مثيل اثيل ثنائي امينالكبريت والسليكون وباستخدام التصعيد ب )،وتحت جو من غاز خامل هو االركون ُشِخصت هذه المعقدات باستخدام التحليل الدقيق للعناصر TMEDA) (CHN) ) وطيف الرنين النووي المغناطيسيH1 وطيف الكتلة مع درجة االنصهار ( فيروسين ، نيوبيوم ، سلينيوم ، كبريت ، غاز خامل ، معقدات عضوية معدنية-:الكلمات المفتاحية