7thInternational Chemistry Conference 12th - 14th November 2018 Riyadh, Saudi Arabia New palladium (II) and silver (I) Schiff base complexes Promising antibiotic and anticancer agents Laila H Abdel-Rahman, Ahmed M Abu-Dief, Azza A Hassan Abdel-Mawgoud
Reflux for 1-3 h at 80 C HNA Stirring H 2 N Reflux 4-6h CHO HO metal salt O OH HN A .2H 2 O N N N O V HO Ag O Pd O H 2 O O O O H 2 O H 2 O O O O HNAAg HNAV HNAPd
Characterization of the prepared imine ligand and their complexes
Characterization of the investigated ligands and their complexes
Fig. 1 : 1 H NMR spectrum of HNA imine ligand • Laila H. Abdel-Rahman, Ahmed M. Abu-Dief, Maram Basha and Azza A. Hassan Abdel-Mawgoud, accepted manuscript, Applied organometallic Chemistry ,2017, e3750. https:// doi.org/10.1002/aoc.3750
Fig. 2: 13 C NMR spectrum of HNA imine ligand. • Laila H. Abdel-Rahman, Ahmed M. Abu-Dief, Maram Basha and Azza A. Hassan Abdel-Mawgoud, accepted manuscript, Applied organometallic Chemistry ,2017, e3750. https:// doi.org/10.1002/aoc.3750
Analytical and physical data of the prepared imine ligands and their complexes Compounds M. wt Color M. p and Analysis (%) (Molecular formula) Yield Dec. temp Found (Calcd.) ( o C) (%) C H N HNA Yellow 74.07 4.40 4.77 C 18 H 13 NO 3 (93) 291.32 280 (74.15) (4.46) (4.81) HNAPd Dark orange 51.34 3.05 3.33 C 18 H 13 NO 4 Pd (90) 413.40 ( >300) ) 52.25) ) 3.14) ) 3.39) HNAV Black 47.99 3.92 3.01 C 18 H 13 NO 5 V (86) 373.94 (>300) ) 47.79) ) 3.98) ) 3.09) HNAAg Light brown 52.03 3.19 3.38 C 18 H 18 NO 6 Ag 451.90 (>300) ) 51.94) ) 3.37) ) 3.37) (91) • Laila H. Abdel-Rahman, Ahmed M. Abu-Dief, Maram Basha and Azza A. Hassan Abdel-Mawgoud, accepted manuscript, Applied organometallic Chemistry ,2017, e3750. https:// doi.org/10.1002/aoc.3750 • Laila H. Abdel-Rahmana, Ahmed M. Abu-Diefa, Moustafa O. Aboelez, Azza A. Hassan Abdel-MawgoudaJournal of Photochemistry & Photobiology, B: Biology 170 (2017) 271 – 285
1.0 1.0 0.9 0.9 0.8 Transmission (%) 0.8 Transmission (%) 0.7 0.7 0.6 0.6 0.5 0.5 0.4 0.4 0.3 4000 4000 3500 3500 3000 3000 2500 2500 2000 2000 1500 1500 1000 1000 500 500 4000 3500 3000 2500 2000 1500 1000 500 -1 ) -1 ) Wave number (cm Wave number (cm FT-IR spectrum of HNAAg complex. FT-IR spectrum of HNA imine ligand. Laila H. Abdel-Rahman, Ahmed M. Abu-Dief, Maram Basha and Azza A. Hassan Abdel-Mawgoud, accepted manuscript, Applied organometallic Chemistry ,2017, e3750. https:// doi.org/10.1002/aoc.3750
The infrared absorption frequencies (cm -1 ) a of the investigated imine ligands and their complexes ʋ (CH) ar υ)OH)/H 2 υ St (-C=N) υ ph (C-O) υ ph (V=O) υ )M -O) υ )M -N) Comp. O HNA 3425 (m) 1613 (s) 3097 1279 (m) - - - HNAPd 3053 (w) 1269 (s) 469 (w) 3423 (s) 1587 (s) - 583 (s) HNAAg 3422 (s) 1589 (s) 3025 (w) 1276 (m) - 568 (w) 497 (w) HNAV 3443 (s) 1593 (s) 3063 (m) 1247 (s) 968 573 (s) 421( m) S = strong, m = medium, w = weak, Ar = aromatic, A = aliphatic, ph = phenolic, As = Asymmetric, S = Symmetric, St = Stretching • Laila H. Abdel-Rahman, Ahmed M. Abu-Dief, Maram Basha and Azza A. Hassan Abdel-Mawgoud, accepted manuscript, Applied organometallic Chemistry ,2017, e3750. https:// doi.org/10.1002/aoc.3750 • Laila H. Abdel-Rahmana, Ahmed M. Abu-Diefa, Moustafa O. Aboelez, Azza A. Hassan Abdel- MawgoudaJournal of Photochemistry & Photobiology, B: Biology 170 (2017) 271 – 285
HNA (II) 2.0 HNAPd HNAVO HNAAg 1.5 Abs 1.0 0.5 0.0 200 300 400 500 600 ,(nm) • Laila H. Abdel-Rahman, Ahmed M. Abu-Dief, Maram Basha and Azza A. Hassan Abdel-Mawgoud, accepted manuscript, Applied organometallic Chemistry ,2017, e3750. https:// doi.org/10.1002/aoc.3750 • Laila H. Abdel-Rahmana, Ahmed M. Abu-Diefa, Moustafa O. Aboelez, Azza A. Hassan Abdel-MawgoudaJournal of Photochemistry & Photobiology, B: Biology 170 (2017) 271 – 285
The stoichiometry and the stability constants of the prepared complexes have been determined spectrophotometrically A X ligand = 0.56 A m K f 2 A 1 C A m 1.8 HNAPd 1.6 HNAV HNAAg-0.1 1.4 1.2 Abs 1.0 0.8 0.6 0.4 0.0 0.2 0.4 0.6 0.8 1.0 [L]/ [L]+[M] Continuous variation plots for the prepared complexes in aqueous-alcoholic mixture at 298 K. Abdel-Rahman, L. H. , Abu-Dief, A. M. , Hamdan, S. K., Seleem, A. A., Int. J. Nano. Chem. 1, No. 2, (2015) 65 - 77. • Laila H. Abdel-Rahmana, Ahmed M. Abu-Diefa, Moustafa O. Aboelez, Azza A. Hassan Abdel- MawgoudaJournal of Photochemistry & Photobiology, B: Biology 170 (2017) 271 – 285 Abdel-Rahman, L.H., El-Khatib, R.M., Abu-Dief, A.M., Abdel-Fatah, S.M., ., J. Photochem. Photobio B. 162, 298 – 308 [2016 ].
Molar ratio method 1.6 1.4 1.2 1.0 HNAAg HNAPd HNAV 0.8 Abs 0.6 0.4 0.2 0.0 0.5 1.0 1.5 2.0 2.5 3.0 [L]/ [M] Molar ratio plots for the prepared complexes in aqueous-alcoholic mixture 298 K. • Laila H. Abdel-Rahman, Ahmed M. Abu-Dief, Maram Basha and Azza A. Hassan Abdel-Mawgoud, accepted manuscript, Applied organometallic Chemistry ,2017, e3750. https:// doi.org/10.1002/aoc.3750 • Laila H. Abdel-Rahmana, Ahmed M. Abu-Diefa, Moustafa O. Aboelez, Azza A. Hassan Abdel-MawgoudaJournal of Photochemistry & Photobiology, B: Biology 170 (2017) 271 – 285
Thermal analysis of the prepared HNA imine complexes Complexes Temperature Fragment loss % Weight loss % o C Molecular formula M. Wt. Found Calc. 33- 171 o C H 2 O 18 4.33 (4.35) 173-380 o C C 7 H 4 O 2 120 29.07 (29.03) HNAPd 382- 563 o C C 11 H 7 N 153 36.99 (37.01) > 563 o C Residue PdO 122.40 29.58 (29.61) 35-187 o C H 2 O 18 4.80 (4.81) 189-373 o C HNAV C 7 H 4 O 2 120 32.11 32.09 375-586 o C C 11 H 7 NO 169 45.16 45.19 >586 o C Residue VO 66.94 17.88 17.90 35- 110 o C 2 H 2 O 36 7.99 (7.97) 112- 191 o C HNAAg H 2 O 18 3.99 (3.98) 193- 377 o C C 7 H 4 O 104 23.07 (23.01) 379- 642 o C C 11 H 8 139 30.77 (30.76) > 642 o C Residue 0.5Ag 2 O+0.5N 2 O 3 153.90 34.05 (34.06)
Kinetic and thermodynamic parameters studies of the prepared metal complexes * log( /( )) 2 W W W AR RT E log log 1 2 * * T E E 2 . 303 RT Decomp. A ∆H * ∆G * ∆S * E * (S -1 ) Complex Temp. (KJmol -1 ) (KJmol -1 ) (KJmol -1 ) (Jmol -1 K -1 ) ( o C) 15.10 42.10 -264.92 102 13.60 89.00 -273.19 276 HNAPd 15.90 0.031 11.97 143.30 -277.68 473 50.80 79.20 -255.88 111 HNAV 49.40 123.50 -263.61 281 51.70 0.10 Δ H* = E* - RT 48.00 176.70 -268.06 480 15.19 31.10 -259.17 72 14.70 44.90 -266.92 113 HNAAg 15.60 0.027 13.20 91.50 -274.61 285 11.40 153.90 -279.45 510 Δ G* = Δ H* - T Δ S • Laila H. Abdel-Rahman, Ahmed M. Abu-Dief, Maram Basha and Azza A. Hassan Abdel-Mawgoud, accepted manuscript, Applied e3750. https:// organometallic Chemistry ,2017, doi.org/10.1002/aoc.3750
Molar conductivity and Magnetic moment measurements Molar conductivity of the prepared complexes at 298 K μ eff (B. M.) Complex Conc. Molar Geometry Mol dm -3 es conductance ᴧ m , Ohm -1 cm 2 mol -1 HNAPd 24.00 Diamagnetic Square planer 1 × 10 -3 HNAV 15.00 1.76 Distorted Square 2 × 10 -3 Pyramidal HNAAg 5.68 Diamagnetic Tetrahedral 1 × 10 -3
pH stability 1.6 1.4 1.2 1.0 Abs 0.8 0.6 HNAAg+0.05 0.4 HNAPd HNAV 0.2 0.0 0 2 4 6 8 10 12 14 pH A. Roth, E.T. Spielberg, W. Plass, Inorg. Chem. 46 , 2007, 4362 – 4364. L. H. Abdel-Rahman, R. M. El-Khatib, L. A. E. Nassr, A.M. Abu-Dief, J. Mol. Struct. 2013 , 1040, 9. L. H. Abdel-Rahman, R. M. El-Khatib, L.A.E. Nassr, A. M. Abu-Dief, F.E. Lashin, Spectrochim. Acta A 2013 , 111, 266-276. L. H. Abdel-Rahman, R. M. El-Khatib, L. A. E. Nassr, A. M. Abu-Dief, A. A. Seleem, Spectrochim. Acta A 2014 , 117, 366. A. M. Abu-Dief and L. A. E. Nassr, J. Iran. Chem. Soc. 2015 , 12 943-955. L. H. Abdel-Rahman, A. M. Abu-Dief, S. K. Hamdan, A. A. Seleem, Int. J. Nano. Chim. 2015 , 1 (2) 65 – 77 L. H. Abdel-Rahman, A. M. Abu-Dief, M., Ismael, M. A. A., Mohamed, N. A. Hashem, J. Mol. Struct. 2016 , 1103, 232 – 244
The suggested structure for the prepared complexes N N O V O Pd O H 2 O O O H 2 O O O .2H 2 O N HO Ag O H 2 O O
Theoretical modeling calculations of HNA imine ligand and its complexes Optimized bond lengths, bond angles and dihedral angles of thestudied complexes using B3LYP/LANL2DZ Angle ( ) Angle ( ) Type of Bond Type of Type of length )Å) bond Angle Angle Pd-N1 1.981 N1-Pd-O1 93.20 N1-Pd-O4 173.1 Pd-O1 2.005 N1-Pd-O2 95.40 O1-Pd-O2 170.1 O2-N1-O1- 2.831 O4 Pd-O2 1.994 O1-Pd-O4 93.63 Pd-O4 2.120 O2-Pd-O4 77.74 V-N1 2.044 N1-V-O1 87.72 O5-V-N1 101.9 V-O1 1.910 N1-V-O2 86.91 O5-V-O1 114.1 V-O2 1.909 O1-V-O4 83.90 O5-V-O2 115.6 V-O4 2.061 O2-V-O4 77.52 O5-V-O4 107.0 11.74 * O2-N1-O1- O4 V-O5 1.598
Calculated lowest total energy (E), highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), energy gap )∆E) and dipole moment )Debye) of imines and their complexes at B3LYP/LANL2DZ. Parameter HNA HNAPd HNAVO Total E (au) -974.230 -1176.07 -1196.04 HOMO (au) -0.2275 -0.2159 -0.2284 LUMO (au) -0.0919 -0.0952 -0.1015 ∆E )eV) 3.6897 3.2842 3.4529 dipole moment 7.900 6.094 6.705 (Debye)
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