حتضري وتشخيص عدد من معقدات ايونات Mn (II), Co (II), Ni (II), Cu (II), Hg (II) مع مزيج من ليكاندات السكارين و حامض الباربيتيوريك و الثايوباربيتيوريك Mn (II), Co (II), Ni (II), Cu (II), Hg (II) :: C.H.N.S H.NMR M(BA) (sac)(h 2 O) 4 M(TBA) (sac)(h 2 O) 4 Cl Cl Mn (II), Co (II), Ni (II), Cu (II) M= BA = Barbituric acid. TBA = Thiobarbituric acid. 206-96 -22-047 -
sac= Saccharine. Hg (II) Hg(BA)(sac) Cl Hg(TBA)(sac) Cl Fahlberg, Saccharin 0 0 (Hsac;,-dioxo-,2-benzothiazole--one;O-benzoicSulfimide) C 7 H 5 NSO O-toluenesulfonamide 59.58 0 878 Fahlberg, Remsen 9 8 0 206-96 -22-048 -
PKa=.60 887 7667 4 US National Toxicology Program 5 777 999 977 6 206-96 -22-049 -
7 C=O S=O N-H 8 Barbituric acide (9) (BA) 2 0 C 4 H 4 N 2 O 864 Barbitursaure 859 kakulus diimide 206-96 -22-05 -
Thio barbituric acide (TBA) 0 TBA C TBA TBA HCV C, malondi aldehyde BA 2 SDI Aldrich Fluka BDH Melting point Elemental Analyzer Apparatus model 06 206-96 -22-050 -
Molar 7 SHIMADZO JENWEAY DMSO Conductivity meter PCM 5 Spectrophoto meter KBR Cintra 5 V. V Visible Souble Deam speatro meter Brucker BM. 6. 4 5 6 Bruker 7 MHZ avance instrument M(BA)(sac) (H 2 O) 4 M = Mn, Co, Ni, Cu, Hg BA = Barbituric acid Cl 0 2 Mn(BA)(sac) (H 2 O) 4 Cl 0 0 2 7677 765 77 7657 7 5 MnCl 2. 4H 2 O 7677 7677 76 77 4 78 7697 Co(BA)(sac) (H 2 O) 4 Cl 2 0 2 206-96 -22-052 -
HgCl 2 7667 7 CoCl 2. 6H 2 O 7677 Ni(BA)(sac) (H 2 O) 4 Cl 0 2 7667 7 NiCl 2. 6H 2 O 7677 Cu(BA)(sac) (H 2 O) 4 Cl 4 0 2 764 7 CuCl 2. 2H 2 O 7677 Hg(BA)(sac) Cl 5 0 2 7 7677 7668 M(TBA)(sac) (H 2 O) 4 M = Mn, Co, Ni, Cu, Hg TBA = Thio Barbituric acid Cl 2 2 Mn(TBA)(sac) (H 2 O) 4 Cl 0 2 2 7677 765 77 765 7 5 MnCl 2. 4H 2 O 7677 76455 7667 7677 4 Co(TBA)(sac) (H 2 O) 4 Cl 8 CoCl 2. 6H 2 O 766 77 9 2 2 2 7677 206-96 -22-05 -
7669 7667 764 8 Ni(TBA)(sac) (H 2 O) 4 8 NiCl 2. 6H 2 O Cu(TBA)(sac) (H 2 O) 4 8 CuCl 2. 2H 2 O Hg(TBA)(sac) Cl HgCl 2 Cl Cl 2 2 7677 4 2 2 7677 5 2 2 7677 Micro Elemental analysis CHNS 0 M.P No. Molecular formula Color Yield% Or Decompo sition [ ]Cl 78 26-265 Element & Metal analyses found. / (calc.)% C H N S 27.95 (28.0).4 (.4) 8.89 (8.6) 6.78 (6.85) 2 [ ]Cl 82 249-250 - - - - [ ]Cl 89 286-289 27.95 (27.62).8 (.) 8.82 (8.8) 6.7 (6.80) 4 [ ]Cl 72 254-256 - - - - 5 [ ]Cl 88 20-20 24.8 (24.2).48 (.5) 7.69 (7.67) 5.87 (5.87) 6 [ ] Cl 9 25-25 - - - - 7 [ ] Cl 67 240-242 26.8.27 8.5.02 (26.62) (.2) (8.59) (.0 ) 8 [ ] Cl 7 2.27 26.8 (26.8).27 (.2) 8.5 (8.60) 9 [ ] Cl 82 58-60 - - - - 0 [ ] Cl 89 262-264 24.9.52 7.92 (25.0) (.50) (7.99) Molar Conductivity Measurement.02 (.0 ) 6.05 (5.98) 2 25) (0 - M) 206-96 -22-054 -
[Hg(BA)(sac)] Cl,[M(TBA)(sac)(H 2 O) 4 ] Cl NO. : 2 5 Complex No. ( (0 - M) [M(BA)(sac)(H 2 O) 4 ] Cl [Hg(TBA)(sac)] Cl 69.00-4.00) DMSO (0 - M) DMSO [Mn(BA)(sac)(H 2 O) 4 ] Cl 40 2 [Co(BA)(sac)(H 2 O) 4 ] Cl 5 [Ni(BA)(sac)(H 2 O) 4 ] Cl 68 4 [Cu(BA)(sac)(H 2 O) 4 ] Cl 50 5 [Hg(BA)(sac)] Cl 66 6 [Mn(TBA)(sac)(H 2 O) 4 ] Cl 4 7 [Co(TBA)(sac)(H 2 O) 4 ] Cl 55 8 [Ni(TBA)(sac)(H 2 O) 4 ] Cl 4 9 [Cu(TBA)(sac)(H 2 O) 4 ] Cl 69 0 [Hg(TBA)(sac)] Cl 54 Magnetic Measurements 5.69,6.0 B.M 7 (2), (4,) (.97,.9 B.M) (II) (.0,2.89 B.M) (II) (II) (II) (II) (.69,2.06 B.M 206-96 -22-055 -
No. ( eff ) ( A ) Complex (Gram Susceptibility) χ g 0-6 c. g. s. u χ M 0-6 c. g. s. u Diamagne. correction 0-6 c. g. s. u χ A 0-6 c. g. s. u (D) ( g ) μ eff B.M. [Mn(BA)(sac)(H2O)4] Cl 0.98 4647.87 7.27 4785.4 6.0 Configuration 2 [Co(BA)(ac)(H2O)4] Cl.24 64.8 7.27 645.45.97 [Ni(BA)(sac)(H2O)4] Cl 7.49 57. 7.27 708.60.0 Octahedral 4 [Cu(BA)(sac)(H2O)4] Cl 2.4 0.82 7.27 69.09.69 5 [Hg(BA)(Sac)] Cl - - - - Diamag. Linear 6 [Mn(TBA)(sac)(H2O)4] Cl 26.8 04.9 47.66 252.59 5.69 7 [Co(TBA)(sac)(H2O)4] Cl 2.5 674.44 47.66 622.0.9 8 [Ni(TBA)(sac)(H2O)4] Cl 6.64 27.2 47.66 48.78 2.89 Octahedral 9 [Cu(TBA)(sac)(H2O)4] Cl.9 589.8 47.66 77.04 2.06 0 [Hg(TBA)(sac)] Cl - - - Diamag. Linear 7 DMSO Electronic Spectra 7 4 M 0 6 S 6 A g 5 (II) (6) t 2 g 5 eg 2 2 4 T g (F) 4 T g (F) 4 T g (F) 4 T 2 g (F) ( ) 7500 2000 cm - 4 A 2 g (F) ( 2 ) 4000 6000 cm - 4 T g (P) ( ) 8000 22000 cm - 206-96 -22-056 -
(t 2 g 6 eg ) (II) 2 Eg (7,2) (II) (26067, (7600,7627cm - ),( 674, 5708 cm - ) 4 T g (F) 4 T 2 g (F), ( 4 T g(f) 4 T g(p) ( 4 T g(f) 4 (7) (II) 2 T 2 g 25027 cm - ) 4 A 2 g(f) NO. Complex Bands v cm - Assignment Suggested Geometry 4 2 4 [Mn(BA)(sac)(H 2 O) 4 ] Cl -- -- Octahedral [Co(BA)(sac)(H 2 O) 4 ] Cl [Ni(BA)(sac)(H 2 O) 4 ] Cl [Cu(BA)(sac)(H 2 O) 4 ] Cl 5708 7627 25027 258 22544 26864 8726 2460 4 T g (F) 4 T 2 g (F) 4 T g (F) 4 A 2 g (F) 4 T g (F) 4 T g (P) A 2 g (F) T g (F) A 2 g (F) T g (P) C.T 2 Eg 2 T 2 g C.T Octahedral Octahedral Octahedral 5 [Hg(BA)(sac)] Cl -- -- Linear 6 [Mn(TBA)(sac)(H 2 O) 4 ] Cl -- -- Octahedral 7 [Co(TBA)(sac)(H 2 O) 4 ] Cl 674 7600 26067 Octahedral 8 [Ni(TBA)(sac)(H 2 O) 4 ] Cl 4284 20009 8 4 T g (F) 4 T 2 g (F) 4 T g (F) 4 A 2 g (F) 4 T g (F) 4 T g (P) A 2 g (F) T g (F) A 2 g (F) T g (P) C.T Octahedral 7499 2 Eg 2 T 9 [Cu(TBA)(sac)(H 2 O) 4 ] Cl 2 g Octahedral 2894 C.T 0 [Hg(TBA)(sac)] Cl -- -- Linear 5 206-96 -22-057 -
[M(BA) (sac) (H 2 O)] Cl M= Mn (II), Co (II), Ni (II), Cu (II) 5 488 54 49 55 BA= Barbituric acid. M-O M-N 68 65 BA C=O 727 [Hg(BA) (sac)] Cl BA= Barbituric acid Hg-N 577 4 C=O 645 7 [ M (TBA) (sac) (H 2 O) 4 ] Cl M= Mn (II), Co (II), Ni(II), Cu(II) TBA= Thio barbituric acid. 9 7 4-40 M-S 5 987 C=S 7 TBA 77 206-96 -22-058 -
5 44 44 N-H TBA [ Hg (TBA) (sac) ] Cl TBA= Thiobarbituric acid 775 C=S 45 M-S 7 TBA 449 N-H 7 الجدول )5( يوضح جرددات حزم االشعة جحث الحمراء لليكاندات والمعقدات المحضرة ) - Cm ( No. of ligand and complexes (C-H) Saccharine (S02) (C=S) (M- (M- S) N) (M O (NH/NH2 Ar Alph V(C0) V(CNS) Sym Asym ) ) Nasac 099w 072w - - 645 s S(6)s As(966)s 45 s 259 s - - - - - BA 285-727 - - - - - - - 52 TBA 292-64 - - - 02 - - - 420 [ ] Cl 08 w 2924 s 672 s 9 s 76 m 26 w - - 540 447 77 m 2 [ ] Cl 0 w 2960 w 65 s 4 m 20 m 256 w - - 54 m 488 s 45 m [ ] Cl 27 w 29 w 68 m 52 s 66 m 2 7 w - - 5 w 462 m 60 s 4 [ ] Cl 2998 m 295 m 67 s 7 m 59 w 259 m - - 55 w 49 m 8 s 5 [ ] Cl 200 m 2978 w 7 s 54 s 80 m 270 m - - 570 s - 60 m 6 [ ] Cl 02 w 2977 w 655 m 40 s 56 m 268 s 00 m 40 w 540 s - 42 s 7 [ ] Cl 000 w 2995 m 645 s 49 s 67 m 284 s 987 m 4 s 557 s - 44 s 8 [ ] Cl 004 w 2990 w 647 s 64 m 5 m 276 m 997 m 424 w 542 w - 424 m 9 [ ] Cl 47 w 2968 m 649 m 6 s 72 m 22 m 982 s Very Weak 582 s - 428 m 0 [ ] Cl 02 w 297 m 657 s 6 s 6 m 266 s 005 s 45 m 50 w - 449 s S = Strong, m = medium, W = Weak, Ar = Aromatic, Alph = Aliphatic (- ppm.4.2 ppm [Hg(TBA)(sac)] Cl (NH) 7-8 ppm 6 0 CH 2 -) 206-96 -22-059 -
[Hg(TBA)(sac)] Cl 4 [Hg(BA)(sac)] Cl ppm.6 (- (NH).6 ppm 7-8 ppm 2 CH 2 -) 206-96 -22-06 -
[Hg(BA)(sac)] Cl 5 [M (BA)(sac)(H 2 O) 4 ]Cl [M (BA)(sac)(H 2 O) 4 ]Cl, M= Mn +2, Co +2, Ni +2, Cu +2. [Complex -4] [Hg(BA)(sac)]Cl 2 206-96 -22-060 -
[Hg(BA)(sac)] Cl Complex 5 [M(TBA)(sac)(H 2 O) 4 ]Cl [M(TBA)(sac)(H 2 O) 4 ]Cl, M= Mn +2, Co +2, Ni +2, Cu +2. [Complex 6-9] [Hg(TBA)(sac)]Cl 4 206-96 -22-062 -
[Hg(TBA)(sac)]Cl Complex 0. I. Remsen, C, Fahlberg, Ber. Dtsch. Chem. Ges., 2, 469(879). 2. I. Remsen, C, Fahlberg, J. Am. Chem. Soc.,, 426(879 880).. E. J Baran and V.T. Yilmaz, Coord. Chem. Rev., 250,980(2006). 4. E. J. Baran. Quim. Nova., 28, 26(2005). 5. M. J. Price, G. C. Biava, L. B. Oser, E. E. Vogin, J. Steinfeld, L. H. Lwy, Science, 67, (970). 6. K. M. A. Malik, S. Z. Haider, M. A. Hossain, M. B. Hursthouse, Acta. Cryst., 40, 696(984). 7. C. A. McAuliffe and W. Leavason, " Phosphine Arsine and Stibine Complexes of Transition Elements" Elesevier Scientific Publishing Company, Nether Lands (979). 8. P. M. Bhatt, N. V. Ravindra, B. Banerjee, G. R. Desiraiu, Chem. Commun., 07 (2005). 9. A. A. Mustafa, M. Sc. thesis, Tikrit University, (205). 0. F. A. Cotton, G. Wilkinson,"Advanced Inorganic Chemistry",6 th ed,. John Wily and Sons, New York,76,(999).. R.K. Lonibala, T. R. Rao, R. K. Dvi, J. Chem, Sci.,8,27, (2006). 2. D. G. Holah and C. N. Murphy, Inorg. Nucl. Chem. Letters, 8, 069-072 (972").. M. Nohoyama, K.Nonoyma, J Inorg. Nucl Chem.,4,2567(98). 4. R.K. Verma, B.K.Mishar, K.C.Satplathy,Asian.J Chem,. 2,65 (997). 5. N. G. Alobaidy, A. M. idtiawe, National journal of Chemistry, Volume, 2, - 2 (2006). 6. B. N. Figis "introduction to Ligand Field", Interscience, New York, 48-49, 258, 9 (967). 206-96 -22-06 -
7. D. Nicholls. "the Chemistry of Iron, Coblt and Nickel" Pergamon press Oxford, 087, 088, 090 09, 09, 5 (975). 8. O. V. Quinzani, S.Tarulli, O. E.Piro, E. J. Baran, E. E.Castellano, Z. Naturforsh., B : Sci., 52, 8 (997) 9. N. A. Dayaaf, M. Sc. thesis, Tikrit university (202) 776 8 7 2. R. M. Ramadan, S.M. EI- Medani, O.A. M. Ali and H. A. Mohmad. J.Coord. Chem.,57,pp.7 (2004). 22. G.L. Hiessler and D. A. Tarr," Inorganic Chemistry" rd ed,. Person Prentce, Hall, International edition, (2004). Abstract This thesis includes, preparation and diagnosis of new twenty-one complex Of ions Mn (II), Co (II), Ni (II), Cu (II), Hg (II) With a mixture of saccharin legends and Barbituric / Thiobarbituric acid. The work included interaction of elements ions above With a mixture of saccharin legends and Barbituric / Thiobarbituric acid with Mole fraction (: : ) (Metal : saccharin : Barbituric or Thiobarbituric acid ) complexes were Diagnosed that have been prepared by fusion degrees, the magnetic sensitivity, careful analysis of the elements (CHNS), molar Electrical conductivity techniques and and infrared spectrum, electronic spectrum and Nuclear Magnetic Resonance spectrum of the proton (H.NMR) techniques. and Through the results that were obtained chemical formulas were suggested for the first part complexes were as follows: - M(BA) (sac)(h 2 O) 4 Cl M(TBA) (sac)(h 2 O) 4 Cl Whereas Mn (II), Co (II), Ni (II), Cu (II) M= BA = Barbituric acid. TBA = Thiobarbituric acid. sac= Saccharine. And it had a octahedral geometric shape Where Saccharine was linked to the central metal by nitrogen atom And Barbituric acid was linked to the central metal by oxygen atom. And Thiobarbituric acid was linked to the central metal by sulfur atom. And complexes Hg (II) have chemical formulas Cl Hg(BA)(sac) Cl Hg(TBA)(sac) With linear geometric structure. Where Saccharine was linked to the central metal by nitrogen atom And Barbituric acid was linked to the central metal by oxygen atom. And Thiobarbituric acid was linked to the central metal by sulfur atom. 206-96 -22-064 -