Equilibrium, kinetic and solvent effect studies on the reactions of [RuIII(Hedta)(H2O)] with thiols (original) (raw)
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0162-0134/ © 2017 Elsevier Inc. All rights reserved. 2 ), 2.54 2.25 (m, 3H, -CH 2 ), 2.64 (m, 1H, CH 2 ), 3.52 (m, 1H, CH 2 ), 3.57 (t, 4H, Gly), 4.17 (t, 6H, CH 3 ), 5.99 (t, 2H, 8.8, Ph), 7.24 (d, 2H, J J 5.7, 4 -MeObipy), ′ 7.45 7.35 (m, 4H, Ph), 7.66 7.48 (m, 5H, Ph), 7.82 7.72 (m, 3H, Ph), ---7.87 (t, 2H, 8.0, Ph), 8.05 7.96 (m, 2H, 4-MeObipy; 2H, Ph), J -8.52 8.49 (d, 2H, -J 2.4, 4-MeObipy; 2H, Ph); 13 C NMR (100.00 MHz, E.R. dos Santos et al. CDCl3 ) 0.06 (d, = 6.9 Hz, 3H, CH δ J 3 , Val), 0.17 (d, = 6.9 Hz, 3H, J CH 3 , Val), 0.42 (d, = 7.1 Hz, 3H, CH J 3 , Val), 0.60 (d, = 6.9 Hz, 3H, J CH , Val), 1.34 1.24 (m, 1H, CH, Val), 1.87 1.66 (m, 2H, pH; 1H, CH, --E.R. dos Santos et al.
Supplementary Information Chem. Commun. 2012 D'Errico et al
All the reagents were obtained from commercial sources (Sigma-Aldrich) and were used without further purification. 1 H and 13 C-NMR spectra were acquired on a Varian Mercury Plus 400 MHz and on a Varian Unit Inova 700 MHz in CD 3 OD or CDCl 3 . Chemical shifts are reported in parts per million (δ) relative to the residual solvent signals: CD 2 HOD 3.31 and CHCl 3 7.27 for 1 H-NMR; CD 2 HOD 49.0 and CHCl 3 77.0 for 13 C-NMR. 1 H-NMR chemical shifts were assigned by 2D NMR experiments. The abbreviations s, bs, d, dd and m stand for singlet, broad singlet, doublet, doublet of doublets and multiplet, respectively. HPLC analyses and purifications were carried out on a Jasco UP-2075 Plus pump equipped with a Jasco UV-2075 Plus UV detector using a 4.60 x 150 mm LUNA (Phenomenex) silica column (particle size 5 µm) eluted with a linear gradient of MeOH in AcOEt (from 0 to 5% in 15 min, flow 1.0 mL min -1 , system A), with a linear gradient of AcOEt in n-hexane (from 0 to 100% in 30 min, flow 1.0 mL min -1 , system B) or using a 4.8 x 150 mm C-18 reverse-phase column (particle size 5 µm) eluted with a linear gradient of MeOH in H 2 O (from 0 to 100% in 30 min, flow 1.3 mL min -1 , system C). UV spectra were recorded on a Jasco V-530 UV spectrophotometer. High Resolution MS spectra were recorded on a Bruker APEX II FT-ICR mass spectrometer using electrospray ionization (ESI) technique in positive mode. Elemental analyses were performed on a Thermo Finnigan Flash EA 1112 CHN analyser. IR spectra were recorded on a Jasco FT-IR 430 spectrophotometer. Optical rotations were determined on a Jasco polarimeter using a 1 dm cell at 25 °C; concentrations are in g/100 mL. Preparative PLC chromatography was performed using F254 silica gel plates (0.5 mm thick, Merck). Analytical TLC analyses were performed using F254 silica gel plates (0.2 mm thick, Merck). TLC spots were detected under UV light (254 nm). For MTS assays the UV absorbance at 490 nm was read using a Beckman Anthos 96 well Microplate Reader.
Journal of Molecular Structure, 2008
The chemistry of Ru(III) complexes containing dmso as a ligand has become an interesting area in the cancer treatment field. Because of this, structural knowledge and chemistry of the moiety Ru(III)–dmso have become important to cancer research. The crystal structures of the compounds mer-[RuCl3(dms)3] (1) and mer-[RuCl3(dms)2(dmso)]:mer-[RuCl3(dms)3] (2) were determined by X-ray crystallography and a speciation of the presence of intramolecular hydrogen bond in these structures has been studied. Compound (1) crystallizes in the orthorhombic space group, Pna21; a = 16.591(8) Å, b = 8.724(2) Å, c = 10.547(3) Å; Z = 12 and (2) crystallizes in the space group, P21/C; a = 11.9930(2) Å, b = 7.9390(2) Å, c = 15.8700(3) Å, β = 93.266(1)°, Z = 2. From the X-ray structures solved in this work, were possible to suggest an interpretation for the broad lines observed in the EPR spectra of the Ru(III) compounds explored here. Also, the exchange interactions detected by EPR spectroscopy in solid state and in solution, confirm the presence of van der Waals interactions such as C–H…Cl in the compounds (1), (2) and (3). The use of techniques such as IR, UV–vis, 1H NMR and EPR Spectroscopy and Cyclic Voltammetry were applied in this work to analyze the behavior of these metallocompounds.
J. Org.Chem. 1983, 48, 995-1000.pdf
J. Org. Chem. the relative ease of formation of the intermediates (IB > I H ) , while the slopes (greater a t lower pH) may reflect the relative ease of trapping of the two intermediates.
Inorganica Chimica Acta, 2006
The interactions of L-cysteine (CysSH) and the tripeptide glutathione (c-L-glutamate-L-cysteine-glycine, GSH) molecules with the trans-[Ru(NH 3 ) 4 (4-pic)(H 2 O)] 2+ ion (4-pic = 4-picoline) have been investigated by cyclic voltammetry, UV-Vis, 1 H NMR, and EPR spectroscopies. Experimental data strongly suggest that the sulfur atom of the SH group, present in CysSH and in GSH molecule, is the binding site of these ligands to the trans-[Ru(NH 3 ) 4 (4-pic)(H 2 O)] 2+ species. The trans-[Ru II (NH 3 ) 4 (4-pic)(CysSH)] +3 and trans-[Ru II (NH 3 ) 4 (4-pic)(GSH)] 3+ ions showed a maximum absorption band at 346 nm (e = 5.0 · 10 3 and 5.4 · 10 3 M À1 cm À1 , respectively) at pH 1.0 attributed to the transition 4d p Ru II ! p*(4-pic). Solutions containing the CysSH and GSH complexes exhibited a reversible electrochemical behavior at pH 7.2 and 7.8 with values of E 1/2 equal to À0.378 V and À0.400 V (SCE), respectively, attributed to the Ru(III)/Ru(II) redox couple. The pK a values measured from changes in the electronic and voltammetric spectra of trans-[Ru II (NH 3 ) 4 (4-pic)(L)] 3+/+2 ions as a function of changes in the hydrogen ion concentration of the solution are, respectively, 5.6 ± 0.1 and 6.6 ± 0.2 for L = CysSH and GSH. The second-order specific rate constants (k 1 and k À1 ) and equilibrium constants (K eq ) values for the reaction (1) (LH = CysSH or GSH) calculated from spectrophotometric data (25 ± 0.2°C, l = 0.20 M NaCF 3 -COO/CF 3 COOH) are k 1 = (4.7 ± 0.2) · 10 À2 M À1 s À1 ; k À1 = (4.4 ± 1.0) · 10 À4 s À1 and K eq(II) = (1.2 ± 0.2) · 10 2 M À1 to CysSH system and k 1 = (5.6 ± 0.2) · 10 À2 M À1 s À1 , k À1 = (5.3 ± 1.4) · 10 À4 s À1 and K eq(II) = (1.1 ± 0.4) · 10 2 M À1 to GSH system.