IB N AL- H AI TH A M J . FO R P UR E & APPL. SC I VO L. 22 ( 4) 2 009 Synthesis and Structural Study of Some Mo(II) Carbonyl Co mplexes with Triazole and Oxadiazole Derivatives Sh. M. H. Obed Departme nt of Chemistry, College of Eduction Ibn-Al-Haitham, Unive rsity of Baghdad Abstract A new carbony l comp lexes of triazole and oxadiazole were sy nthesized. These comp lexes were identified and their st ructural geometric were suggested by using FT -IR and UV-Vis sp ectra, conductivity measurements and other chemical and p hy sical prop erties. The sp ectra data (FT -IR, UV, Vis.) with the substantial aid of group theoretical calculations gave so many evidences for the p rop osed geometries and the ty p e of bonding of these compounds Introduction Transition metal carbony l comp lexes are the basic st arting materials for the sy nthesis of many organometallic comp ounds, which are mainly used as cataly st s for the reactions of unsaturated hy drocarbonates[1-4]. Heterocy cles and in p articular the five-membered rings e.g. mercap to derivatives of triazole and oxadiazole have received more att ention during the last decades as bioactive moieties and of industrial app lication of these rings [5-7]. Also,t hey were included in many basic st ructures of drugs and imp ortant ones of octane numbers [8]. Furt her, the triazole and oxadiazole derivatives were suggested that (-SH) group att ached to heterocy clic nucleus may induce fungicidal activity [9,10]. The interaction of these rings with metal carbony l comp lex gives a great interest for versatility and diversity form the p oint of structural, biological and catalytically esp ects. Also, beside their useful app lication, they have the effect on the coordination nature of the resulted ones, esp ecially the olefinic group in the triazole structure is a good coo rdinating moiety may link to number of metal ions forming organometallic comp ounds st ructure [11]. Also, subsequently nature of bands and numbers of CO group were attached to metal [12,13]. Hence, the p resent work invest igated the reaction of the three ligands from the Bis - triazole and Bis-oxadiazole derivatives with carbony l group s M o(CO)4bipy was p repared from the reaction of 2,2'-bipy ridly with M o(CO)6 under in an atmosp here of nitrogen to formaly a new carbonyl complexes. According, the characterization of these comp lexes would be p resented and the results would be discussed with sp ectroscop ic invest igation, p hy sical techniques group theoretical calculations. Experimental Materials All chemicals used were of highest p urity available. Physical Me asurements M elting p oints were recorded uncorrected of Stuart melting p oint app aratus. FT-IR sp ectra were obtained by using Sh imadzu FT-IR-8400 Sp ectrop hotometer in the rang (4000- IB N AL- H AI TH A M J . FO R P UR E & APPL. SC I VO L. 22 ( 4) 2 009 200) cm-1, U.V-Vis sp ectra were recorded by using Sh imadzu UV-160A Sp ectrop hotometer in CHCl3 solvent in the rang (200-700) nm. Conductivity measurements were obtained by PW 9525 digital conductivity meter. Preparation of Compounds Preparation of the ligands 1- Prep aration of (OTRZ) [4,5diphenyl-3(2-prop y ny l) thio1,2,4-triazole]. (OT RZ) was p repared from ethy l benzoate as according to the literature method [11] and as shown by scheme (1). S cheme (1) 2- Prep aration of (TRZ) [bis(4-p heny l-3-thiol-1,2,4-trizaole 5yl)butane]. (TRZ) was p repared following general p rocedures decribed in the literature [14] as shown in scheme (2). S cheme (2) 3- Prep aration of (OXZ ) [bis(3-thiol-1,3,4-oxadiazole-5yl) butane]. (OXZ) was p repared by a modified literature method [15] and as shown in scheme (3). . S cheme (3) IB N AL- H AI TH A M J . FO R P UR E & APPL. SC I VO L. 22 ( 4) 2 009 Preparation of the Metal Carbonyl Complex [Mo (CO)4 bipy] (M) Tetra carbony l mono -2,2'-bipy ridyl moly bdenum (O) was p repared according to the literature method [16]. The mixture of M o(CO)4 (53mmole, l.4g) and bipy ridyl (5.12mmole,0.8g) were refluxed in toluene (50ml) for l.5hr under N2. Aft er cooling, the red cryst alline comp lex was washed with a mixture of toluene, (15ml) and light p etroleum (30ml) and dried under vacuum. The product was stable toward air and moisture, soluble in p olar solvents but insoluble in petroleum sp irit and water. Preparation of the Mixed Ligand Carbonyl Comple xes. [Mo II (CO )3 bipy (OTRZ)]I2 (MI), [Mo I I (CO )3 bipy (TRZ)] I (MII) an d [Mo II (CO )3bipy (OXZ)]I ( MIII) These comp lexes were p repared by dissolving M o(CO)6bipy (0.16mmole) in chloroform (50ml) then treated with iodine (0.40mmole,0.1g) in (25ml) chloroform with st irring at OC o , the bright orange mixtures were obtained. (OT RZ) (0.32mmol,0.09) and (TRZ) (0.32mmol,0.13g)dissolved in (10ml) chloroform while, the (OXZ ) (0.32mmole,0.09g) dissolved in (1:1) ml of a (chloroform /ethanol ) mixture were added drop wise, st irring at OC o for 6hr., then the solvent was slowly evap orated to obtain nicely colored cry st als. These comp lexes are st able in air, have high melting p oints as shown in table (1) and soluble in DM F and CHCl3 solvents but insoluble in water. The comp lexes were indentified by sp ectral (FT -IR and U.V) and p hy sical methods. Table (1,2). Re sults and Discussion Spectroscopic Characterization of New Complexes Vibrational Spectra The characterist ic (FT -IR) bands observed and the vibrationl assignment of the ligands and their metal complexes are exp lained in detail in tabled (2). The sp ectrum of (OTRZ) is characterized by the presence of an essential band which belon gs t o the olefinic group at (1630cm -1 ) and other bands at (965 & 885 cm -1 ) which was originated out of the plane bending v ibration of the vinylic group , where the sp ectrum of the comp lex (M I) shows red shifts of the olefinic band absorp tion to (1550um -1 ) and to (925&832cm -1 ) for the viny lic CH2 group , which indicate -bonding between the metal and olefinic group [17], this was further indicated by the app earance of (M o-C) band absorpt ion, table (2). A comp arison of the IR sp ectrum of the ligands (TRZ and OXZ ) and their complexes leads to the medium -SH band of the ligands at (2530& 2560cm -1 ) resp ectively, which disapp ear indicating the disp lacement of hy drogen SH by means of metal ion. The  C=N+C=S band of the (TRZ) at (1270cm-1) is sp litted on coordination at (1310&1253 cm -1 ) while , the (OXZ ) showed two distinct p eaks,t he first one at(1315cm -1 ) and the second at (1250 cm -1 ) red shift in comp lex to (1570 cm -1 ) which could be att ributed to C=N st retching . This account for the C=N and sulp hur that coordinated to the metal ion [18-21]. The app earance of new bands in the IR sp ectra of these comp lexes in table (2) is p rop ably due to the formation of (M -C), (M -N) and (M -S) developed through comp lexation (21) . IR S pectra for Carbonyl Groups of (MI, MII an d MIII) and The ir Group The oreti cal Cal culations S cheme (5) IB N AL- H AI TH A M J . FO R P UR E & APPL. SC I VO L. 22 ( 4) 2 009 The comp ound st udied in the present work is of the formula [M o (CO)4 bipy ] , where (M ) is bipy either monodentate or bidentate nitrogen donor. Hence, the bidentate ligand must belong to the C2v group [12,22],while the geometrical isomer is shown in scheme (4). Theoretically ,the cis-isomer should give four IR bands, the sp ectra of the p repared (M ),showed four p rinciple bands in the region(2000-1825)cm -1 in table(2), fig(1), which can be assigned to t erminal  CO virbrations. The presence of four bands indicated cis- isomeration. for the bidentate bip y comp lex . . First of all, it was found t hat t he CO sp ectral band position for M o comp lexes, showed that all the CO group s t o be terminal, no bridging CO exist in fig (2). The prepared comp lexes are contain three Carbonyl group s which may have facial configurations. The point group for the molecules is Cs,while the p oint group considering for CO moieties is C3v for facial configuration and the main axis of sy mmetry is shown in scheme (5). According to the group theoretical calculations based on C3v p oint group s, t he number of CO vibration modes were calculated and the results are shown in table (3). The CO st retch of the E mode (C3v) sp lits A' and A'' comp ounds characterist ic of the overall molecular sy mmetry of Cs, this was the case for the comp lex (M I), i.e. three carbony l bands, due to 2A',/A''modes were found . The other comp lexes show only two bands as in the case of compounds (M II, M III), this is because the two close-lying bands due to A +E modes were observed. Generally the E mode is the lower frequency band [23,24]. Electroni c S pectra M any carbony l comp ounds of group VIB elements of the p eriodic table were st udied [24,25]. Gray and Beach [26,27] measured the UV absorp tion sp ectra of M (CO)6 of group VIB elements and assigned the band on the M OT basis. The new comp lexes are conducting and most diagnost ic bands, their assignments are shown in table (4), fig (3). The used solvent is chloroform ,causes blue shift for all absorp tion bands, the characterist ic in the sp ectra of the comp lexes is the app earance of a new band at around (27.470)cm -1 which is not found in the sp ectrum of the p arent (M ) , this is assigned as I L' ( * ) for donor moieties of legends (olefin, nitrogen and sulfur atoms). The absorp tion bands in high energy region can be assigned to t he two comp onents of ( * ) transitions of carbony l group s .Besides that, the LF transition can't be assigned easily, since they may be overlap with that of ( * ) absorp tion bands [24,28,29]. S ch e me ( 4 ) IB N AL- H AI TH A M J . FO R P UR E & APPL. SC I VO L. 22 ( 4) 2 009 The general formula of the p repared comp lexes can be depicted as shown in table (1) and the p rop osed st ructures p entagonal bipy rmidal for the selected complexes can be given as follows: M I Wh e re R= IB N AL- H AI TH A M J . FO R P UR E & APPL. SC I VO L. 22 ( 4) 2 009 Re ferences 1. Borg, S.J.; Bondin,M .I. ; Best ,S.P. ; Razavet,M .; Liuand X. and Pickett,C.J. (2005), Biochemical So ciety Transactions Vol.33(1). 2. Okay ran, S. O.; Kay ran,C. and Kreiter,C. G. (1992),Organomet J. Chem., 434:79. 3. Rigaut,S.; Touchard, D. and Dixneuf, P.H. (2003), J.Organomet.Chem.,684:68. 4. Ammar,H.B.; Lenotre,G.; Salan, M .; Kaddachi, M .T .; Toup et,L.; Renaud,J.L.; Bruneau ,C. and Dixn euf, P.H. (2003), Eur.J.Inorg.Chem.,4055. 5. Jassim, A.H. (1993), Ph. D. Thesis,Al-Nahrain University of Engineering and Science Iraq. 6. Rasol N.(1987),M . Sc. Thesis, University of Baghdad ,Iraq and References Cited Therein. 7. AL-Zahawi,S. K. A.(1986), M . Sc. Thesis, University of the Baghdad Iraq . 8. Vahren Kemp,H. (1975), Angew. Chem. Int. Ed. Engl.,14:322 . 9. GreenWood ,N.N. and Earnshaw, A. (1998) "Chemist ry of the Elements"Second Eddition , Pergamon Press. 10. Nesmeyanov ,A. N. and Nesmeganov, N.A . (1981),"Fundamental of Organic Chemist ry " Vol. III, M ir Publishers, M oscow. 11. M ishar ,L. and Anjali, Jha, (1996) Indian J. of Chemist ry ,35A: l00l. 12.Cottonn ,F. A. and Willkinson ,G.S. (1987),"Advanced Inorganic Chemist ry " Acomprehensive Text, Fifth Eddition, John. Wiley . 13. Abbas,M . H. (1991) Ph. D. T hesis, Not tingham. 14. M usa, F.H. (1998),Iraqi :J.of Chem.,Vol.24 (2). M I I M I II Wh e re R'= Wh e re R''= IBN AL- HAITHAM J . FO R PURE & APPL. SC I VO L. 23 (1) 2010 15. M usa,F.H. ; M ahmoud ,M .J. and M ust afa,I.F. (2002),Ibn Al-Haitham , J.for Pure and Ap p l . Sci ., Vol . 15(3):44. 16. Stiddard,M . H. B. (1962) J. Chem. .Soc., 4712. 17. Nakamoto, K. (1997)," Infrared Sp actro of Inorganic and Coordination Comp ounds", 6t h. Ed. Wily , Intersience, New York. 18. Al-Obaidi, E. Z. M .; Nadir,K. M . and Eur. Roche, V. E .(1991)J. M ed. Chem., 26. 19. Singh, B. and Singh, R. D. (1977), J. Inorg. Chem ., 39: 25. 20. M ust afa,I.F. ; At to , A.T . and M usa, F.H. (1991),Iraq J.Chem., 16. 21. Dilsky Stefan and Schenk Wolfdieter,A. (2006) , Z.Naturforsch , 61b:570 . 22. ACot ton,F. (1971)."Chemical Ap p lication of Group Theory"2nd.Ed.New York,Wiley Interscience. 23. Tripath ,S. C. and Srivast ava ,S. C. (1970) J. Organomet. Chem., 25:193 . 24. Stoeffler,H.D.; Thornton,N.B.; Temkin, S.L; Schanze, K. S. (1995),J.Am.Chem. Soc., 117:7119 25. George, M .W. and Turner, J.J. (1998),Coord.Chem.Rev.,177:201. 26. Gray , H. B. and Beach,N.A. (1963) J. Am. Chem. Soc., 85:2922. 27. Beachand,N.A. and Gry a,H.B. (1968),J.Amer.Chem .Soc.,90:5713. 28. Friedman,A.E.; Ch amborn,J.C.; Sauvage,J.P.; Turro N.J. and Barton,J.K. (1990),J.Am.chem.soc.,112:4960. 29. Geoffroy ,G.L. and Wrighton, M .S. (1979) "Organometallic Phot ochemist ry " Academic Press. New York. Table (1) Some Physical Properties of [Mo(CO)4bipy] . (M) and new Prepared Complexes Col our M.P.(C o ) %Yield Chemical Formula M Red (189-191) 95 C14H8N2O4Mo MI Deep brown (244-246) 77 C30H21N5O3S MoI2 MII Orange (280- 282)dec. 75 C33H28N8O3S 2MoI MIII Brown (174-176) 87 C21H18N6O5S 2MoI ` IBN AL- HAITHAM J . FO R PURE & APPL. SC I VO L. 23 (1) 2010 Table (3) CO Vibrational Modes and their assignments for Cis-Mo (CO)4- bipy an d fac. Mixed ligand Molybdenum tri-carbonyl compounds Compound A1 (2) A1 (1) B1 B2 M 2012 1918 1887 1820 Compound A1 A' A" MI 1967 1910 1869 Compound A1 E MII 1991 1870 MIII 1992 1890 Where L= bipy ridyl (bip y ) L'= triazole or oxadiazole group Table (4): Electronic Spectra and Conductance (in CHCl3) for Metal Carbonyl Complexes Fi g . ( 1) : T he sele cte d C O ba n ds of te t ra ca bo n yl s ( M o ) in t he st ret chi n g re gi o n Band nm (cm -1 ) Band nm (cm -1 )(M) Assignm ent MI MII MIII Assignm ent sc m -1 486(20.576) MoL CT 366(27.322) 365(27.397) 361(27.700) *IL' 80 370(27.027) *IL 331(30.211) 343(29.154) 343(29.154) Mo* CO CT 50 343(29.154) Mo* CO CT 255(39.215) 259(38.610) 254(39.370) Mo* CO CT 50 256(39.062) Mo* CO CT IBN AL- HAITHAM J . FO R PURE & APPL. SC I VO L. 23 (1) 2010 Fi g . ( 2) : S ele cte d C O ba n d o f M o co m pl e xe s in the CO s t re t chi n g re gi o n Fig. (3):Absor ption spectra of Mo(CO)4 bipy and their complexes in chloroform sol vent لصرفة والتطبیقیة المجلد ا لوم لهیثم للع ن ا 2مجلة اب 2) 4 (2 0 0 9 تحضیر ودراسة تركیبیة لبعض معقدات كاربونیالت مع مشتقات الترایازول واالوكسادایازول) II(المولبیدینیوم شذى محمد حسن عبید قسم الكیمیاء، كلیة التربیة ابن الهیثم، جامعة بغداد الخالصة زول واالكــسادایازول الكاربونیلیــة الجدیـدة الحاویــة علــى مــشتقات الترایــاعــدد مــن المعقــداتحـضرت الفیزیائیــة المناســبة بطیــف االشــعة تحــت الحمــراء واالشــعة ائقتــم تشخــصیها واقتــراح شــكلها الهندســي بــالطر . الكیمائیة القیاسیة والخواص الفیزیائیةائقًفوق البنفجسیة المرئیة، التوصیلیة الكهربائیة فضال عن الطر المرئیـة مـع الحــسابات -ء واالشـعة فـوق البنفــسجیةاعطـت نتـائج الدراسـة بطیــف االشـعة تحـت الحمــرا النظریــة باســتخدام نظریــة المجموعــة بــراهین اضــافیة مهمــة للــصیغ التركیبیــة المفترضــة ونــوع االرتبــاط فــي .هذه المركبات