Research Journal of Chemical Sciences ______________________________________________ ISSN 2231-606X Vol. 4(8), 12-16, August (2014) Res. J. Chem. Sci. International Science Congress Association 12 Synthesis and Characterization of Bis(cyclopentadienyl)Zirconium(iv)Bis (o,o-dialkyl and alkylenedithiophosphate) ComplexesHussien A.R. Department of Chemistry, Al-Aqsa University, Gaza Strip, Palestinian National Authority, ISRAELAvailable online at: www.isca.in, www.isca.me Received 9th May 2014, revised 28th May 2014, accepted 16th August 2014Abstract CpZr[SP(OR)2 (where R = C5-, CHCHCH2-, (CHCH-, (CHC- and C-), CpZr[SPOGO] (where G = – CHC(CHCH–, –CHC(CCH– and –C(CHC(CH–) have been synthesis by the reaction of Bis(cyclopentadienyl) zirconium(iv)dichloride with O,O-dialkyl and alkylenedithiophosphoric acidsin molar ratio1:2 in refluxing benzene. All products were yellow solids, soluble in organic solvent, monomeric in nature and have been characterized by elemental analyses, molecular weight determinations, and have been further characterized by some spectroscopical data IR and NMR (H, 13C and 31P). Keywords: Zirconium, alkylene dithiophosphoric cyclopentadienyl, complexes, ligand.IntroductionZircanocene complexes are amongst the most widely used transition metal complexes. Over last several decades, they have been utilized for a variety of applications, such as catalytic properties of zirconium metalocenes, and in the development of modern synthetic methodology of such complexes has been demonstratedO,O-dialkyl and alkylenedithiophosphoric acids act as versatile bidentate dithio ligands and form a variety of stable complexes with transition2,3 and non transition4-7elements. The preparation and structure of metal dithiophosphate has received considerable interest during one half decades due to their application in the area of antioxidants, anti wear8,9 and pesticides10,11. Material and MethodsMoisture was carefully excluded throughout the experimental work, solvents were dried according to the standard methods prior to their use. Distilled Glycols were use, Bis (cyclopentadienyl) zirconium (iv) dichloride (Aldrich) was used as supplied, Dialkyl and alkyleneditiophosphoric were synthesised as describe in the literature12-13. Sulfur was estimated as BaSO4 (Messenger's method). IR spectra were recorded in KBr mulls in the range 4000-400 cm-1 on a Perkin Elmer= 377 spectrophotometer. The H, 13C and 31P NMR spectra were recorded on a Bruker DRX 300 (120 MHz) spectrometer using TMS as the internal reference. Reaction of Bis (Cyclo Pentadienyl Zirconium (iv) Dichloride with Dialkyl (OPr-n) and Alkylene Dithiophosphoric acids in 1:2 Molar Ratios: HSP(OPr-n)(0.219 g) was dissolved in 10 ml benzene and was added drop wise with stirring to a solution of CpZrCl (0.150 g)in 15 ml benzene. The reaction mixture was refluxed for 5 hour at 25C. The colorless reaction mixture changed to yellow color. Vacuum was used to remove the excess solvent. Finally the yellow product was washed with n-hexane and dried in vacuo. Results and Discussion Bis(cyclopentadienyl) zirconium(iv) Bis(O-Odialkyl and alkylene dithiophosphate) derivatives have been synthesized by the reaction of dialkyl and alkylenedithiophosphoric acids with Bis(cyclopentadienyl) zirconium(iv) dichloride. All these reaction carried out under refluxing in benzene for 6 h, in 1:2 molar ratio as in equation 1 and . CpZrCl + 2HSP(OR)2 CpZr[SP(OR)+2HCl (1)Where R = C-, CHCHCH2-, (CHCH-, (CHC- and - CpZrCl + 2HSPOGO CpZr[ SPOGO ]+2HCl (2)G = – CHC(CHCH–, –CHC(CCH– and –C(CHC(CH–. The colorless reaction mixture has been changed to yellow. These newly synthesized Bis (cyclopentadienyl) zirconium (iv) Bis (dialkyl and alkylene dithiophosphate) complexes are yellow colored crystalline solid, non-volatile in nature, freely soluble in common organic solvents, and extremely sensitive towards atmospheric moisture. The molecular weights of all derivatives were determined and tabulated in table 1, which indicated that all of them are in monomeric form. IR Spectra: On the bases of recent reports14 IR spectra of the new derivatives was analyzed. The IR spectra recorded in the region 4000-400 cm-1. The S-H stretching band at 2544 – 2400cm-1 which has been observed for the parent acid15 disappeared Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 4(8), 12-16, August (2014) Res. J. Chem. Sci. International Science Congress Association 13 in the derivative spectra as a result of formation of Zr-S. A new band14 for Zr-S appeared in the region 402-440 cm-1. Two bands corresponding to (P)–O–C and P–O–(C) vibration at the region 974.0–1099.0 cm-1 and 810.0 – 889.1 cm-1 respectively16A band in the region 912.3 – 940.0 cm-1 is the most probably due to dioxaphospholane and dioxaphosphorinane ring vibrations.17-18 A sharp band present in the region 630.7– 684.7 cm-1 can be assigned to P=S vibrations16. Bands in medium intensities in the region 505.3– 580.0 cm-1 attributed to P–Sasymmetric and symmetric vibrations19. Detailed peak data is recorded in table 2. H NMR Spectra: The NMR spectra of all derivative complexes recorded in CDLtable 3, show the characteristic resonance due to alkoxy and glycoxy (dithio moiety) protons. The singlet peak at (3.1- 3.5ppm20 of the SH proton is absent in the spectra of all derivative complexes which means disappearance of S-H bond and formation of Zr -S bond. 13C NMR Spectra: The 13 NMR spectra of all derivative complexes were recorded in deutrated chloroform at ambient temperature. Table 4 Shows small chemical shifts to those obtained spectra for the parent dithiophosphoric acids that indicates no substantial change in the structure. Table-1 Analytical and Physicochemical Data for Some New Products SI. No. Compounds Physical State M. P. C Mol. Wt. Found / (Calc.) % S %Zr Found / (Calc.) I CpZr[SP(OC 2 Yellow solid …..578 /(591.78) 20.53/(21..67) 14.10 /(15.41) II CpZr[SP(OCHCHCH2 Yellow solid 155 …... /(647.89) 18.78/ (19.80) 13.44/(14.08) III CpZr[SP(OCH(CH2 Yellow solid …… 634/ (647.89) 18.60 / (19.80) …./(14.08) IV CpZr[SP(OC(CH Yellow solid …… 689 / (704.00) …… / (18.22) 12.10./(12.96) V CpZr[SP(OC Yellow solid ……. …... / (783.96) 15.50 / (16.36) ……/(11.64) VI CpZr[SPOCHC(CHCHO] Yellow solid 143 602/ (615.62) 20.11 / (20.83) 14.00../(14.82) VII CpZr[SPOCHC(CCHO] Yellow solid 136 663 / (671.72) 18.21 / (19.09) 12.70/(13.58) VIII CpZr[SPOC(CHC(CHO] Yellow solid 189 630 / (643.68) 18.30 / (19.99) 13.50/(14.17) Table-2 IR Spectral Data (cm-1) for Some New Products SI. No. Compounds P-O-(C) (P)-O-C Ring Vibration (Zr-S) P=S P–S I CpZr[SP(OC 2 810.0 s 1016.4 s -- 405.0 m 655.8 m 540.0 m II CpZr[SP(OCHCHCH2 850.5m 993.0 s -- 440.0 w 630.7 m 543.9 m III CpZr[SP(OCH(CH 889.1 m 974.0m -- 402.0 m 651.9 m 542.0 m IV CpZr[SP(OC(CH 820.0 s 990.0s -- 413.0 w 650.0 m 532.0 m V CpZr[SP(O C 820.8 s 1099.0 m -- 422.0w 670.5 s 513.0w VI CpZr[SPOCHC(CHCHO] 815.8 m 1056.9 s 912.3 m 410.0 w 684.7 m 505.3 m VII CpZr[SPOCHC(CCHO] 830.0 m 1020.2 s 940.0 m 407 0 m 660.0 m 530.0 m VIII CpZr[SPOC(CHC(CHO] 858.3 s 1010.6 s 923.8 m 409.0 m 661.5 m 580.0 m b = broad, s = strong, w = weak and m = medium absorption bands Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 4(8), 12-16, August (2014) Res. J. Chem. Sci. International Science Congress Association 14 Table-3 H and 31P NMR Data for Some New Products SI. No. Compounds 1 H chemical shift in 31 P chemical ppm in CDCl shift in ppm (parent acid) I CpZr[SP(OC1.188 – 1.288, m, 12H(CH) 4.062– 4.12, m, 8H(OCH) 6.42 –6.56, m, 10H(C 5 H 5 ) 86.13 (85.700) II CpZr[SP(OCHCHCH0.764 – 0.857, m, 12H(CH) 1.341 – 1.364, d, 8H(CH) 3.375– 3. 561 m, 8H(OCH) 6.193 – 6.483, m, 10H(C 5 H 5 ) ……(86.100) III CpZr[SP(OCH(CH1.219– 1.270, m, 24H(CH) 4.402 – 4.423, m, 4H(OCH) 6.326 – 6.521, m, 10H(C 5 H 5 ) 83.56 (82.300) IV CpZr[SP(OC(CH0.788– 0.887,m, 24H(CH) 1.728,s, 4H(CH) 3.460 – 3.709, m, 8H(OCH) 6.309 –6.475, m, 10H(C 5 H 5 ) ……(85.700) V CpZr[SP(OC6. 236 –6.881, m 10H(C5 7.004-7.440,m,, 20H(OC 6 H 5 ) ……. (79.900) VI CpZr[SPOCHC(CHCHO]0.828-1.126.,m, 12H(CH) 3.705 – 3.756,m., 8H(OCH). 6.354- 6.533, m, 10H(C 5 H 5 ) 77.93 (77.300) VII CpZr[SPOCHC(CCHO]0.615, m,0.804,12H(CH) 1.117 – 1.539, m, 8H(CH) 4. 022 – 4.203,m, 8H(OCH), 6.280– 6.412, m, 10H(C) ……(78.500) VIII CpZr[SPOC(CHC(CHO]1.065-1.438, m, 24H(CH) 6.451 – 6.576 m, 10H(C 5 H 5 ) 93.72 (93.100) s = singlet, d = doublet, t = triplet, q = quartet m = multiplet . Table-4 13C NMR Data for Some New Products SI No. Compound 13 C Chemical shift, in ppm C CH CH 2 CH 3 CO C 5 H 5 I Cp 2 Zr[S 2 P(O C 2 H 5 ) 2 ] 2 …. …. …. 15.913s 63.338 s 128.162s II CpZr[SP( OCH(CH …. …. …. 23.192s 72..472s 117.344-118.023 d III Cp 2 Zr[S 2 POCH 2 C(CH 3 ) 2 CH 2 O] 2 32.981 s …. …. 19.953-21.311,t 77.066-77.169 d 117.489 s t = triplet d = doublet and s = singlet 31P NMR Spectra: The proton decoupled 31 NMR spectra Bis(cyclopentadienyl) zirconium(iv) Bis(dialkyl and alkylene dithiophosphate) derivatives table 3shows that each derivative have only one signal peak between 93.72 – 77.93 ppm. Similar peak indicating that all the derivative molecules contain only one type of phosphorous nucleus. However, no notable difference was observed in comparison to the parent acids21. It appears that small shift in 31P this shifting according the Glidewell observations indicates bidentate behavior of the ligand22. Structural Elucidation: IR spectra, (H, 13C) NMR, molecular weight determination and elemental analysis indicate that the ligand is a bidentate ligand. Monomeric nature of the complexes was also approved. From the above data the suggested structure for the produced is shown in figure 1. Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 4(8), 12-16, August (2014) Res. J. Chem. Sci. International Science Congress Association 15 Figure-1 Suggested structure of Bis(cyclopentadienyl)zirconium(iv)- Bis(O-Odialkyl and alkylene dithiophosphate) complexes ConclusionThe derivatives of the complex Bis (cyclopentadienyl) zirconium(iv) Bis(dialkyl and alkylenedithiophosphate were synthesized. They were all yellow colored solid, non-volatile, freely soluble in common organic solvents and sensitive towards atmospheric moisture. 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