Bull. Chem. Soc. Ethiop. 2006, 20(2), 227-234.

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ISSN 1011-3924 © 2006 Chemical Society of Ethiopia

NON-BRIDGING LIGAND EFFECTS ON THE KINETICS OF REDUCTION OF CHLORO- AND AZIDO-PENTAAMMINECOBALT(III) BY SOME POLYPYRIDYL COMPLEXES OF RUTHENIUM(II) Olayinka A. Oyetunji*, Maipelo Gabalebe, and Ngonye Sabure Department of Chemistry, University of Botswana, Private Bag UB 00704, Gaborone, Botswana (Received November 19, 2005; revised April 28, 2006)
ABSTRACT. Pentaamminecobalt(III) complexes, [Co(NH3)5X]2+ (X = Cl-, N3-), are reduced by [Ru(bipy)3]2+ and [Ru(terpy)(bipy)Cl]+ in aqueous media at a constant ionic strength of 0.5 M (HCl/LiCl). At 308 K, the second order rate constants (M-1 s-1) are as follows: 17.9 for the reduction of the azidocobalt(III) complex by [Ru(bipy)3]2+, and 1.41 and 2.63 for the [Ru(terpy)(bipy)Cl]+ reduction of the azido- and chlorocobalt(III) complexes, respectively. Activation enthalpies (∆H≠) and entropies (∆S≠) were determined from temperature dependence measurements with the following results: ∆H≠ = 72.1 kJ mol-1 and ∆S≠ = 13.3 J mol-1 K-1 for the [Ru(bipy)3]2+ reduction of the azidocobalt(III) complex, while for the reduction of the cobalt(III) complexes by [Ru(terpy)(bipy)Cl]+, ∆H≠(N3-) = 20.3 kJ mol-1, ∆H≠(Cl-) = 40.6 kJ mol-1, ∆S≠(N3-) = -177 J mol-1 K-1, and ∆S≠(Cl-) = -106 J mol-1 K-1. The relative rates of electron transfer in the different reactions and the influence of π-acceptor ligands on the ruthenium(II) reduction of the cobalt(III) complexes are discussed. KEY WORDS: Non-bridging ligands, Pentaamminecobalt(III) complexes, Azidocobalt(III) complex, Chlorocobalt(III) complex, Kinetics of reduction of cobalt(III) complexes, Ruthenium(II) polypyridyl complexes,

INTRODUCTION A great amount of work has been done on the substitution and redox properties of ruthenium(II and III) complexes [1-3]. This is partly connected with the discovery that some of these complexes, e.g. cis-[Ru(NH3)4Cl2]Cl, α-[Ru(azpy)2Cl2], mer-Ru(terpy)Cl3] and [Ru(phen)3]2+ have antitumour activity [4, 5]. This property among others has led to increased interest in the study of their chemical characteristics. Ruthenium(II) cations like [Ru(NH3)6]2+, [Ru(NH3)5H2O]2+ and [Ru(en)3]2+ have been classified as typical outer-sphere reductants [1, 6, 7], basically as a result of their substitution inertness and redox potentials, while [Ru(tppm)(dpp)H2O]2+, [Ru(tpmm)(DPMet)H2O]2+ and [Ru(tpmm)(DPPro)H2O]2+ are known to be labile as a result of introducing different spectator ligands [8]. Bridging ligands and nonbridging ligands can play significant roles in the reactivities of the complexes. As the reactivity is affected, it is expected that their antitumour activity will also be affected by the nature of the ligands surrounding the metal ion. Most cobalt(III) complexes are low-spin and inert and so most reactions between cobalt(III) and ruthenium(II) complexes proceed rather slowly. However, the identities of ruthenium(II) reductants significantly affect the rates of reduction of cobalt(III) complexes [3]. This work investigates the effect of non-bridging ligands on the redox properties of ruthenium(II) and looks at the reactivity patterns of their pentamminecobalt(III) oxidants. EXPERIMENTAL Materials. [Ru(terpy)(bipy)Cl]Cl was prepared according to the method described by Meyer and co-workers [9], which involved initial synthesis of [Ru(terpy)Cl3]. This complex was then reduced to [Ru(terpy)(bipy)Cl]Cl by reaction with bipyridine in the presence of triethylamine. Electronic and infrared spectra gave peaks which agreed with literature values [9, 10].
__________ *Corresponding author. E-mail: oyetunji@mopipi.ub.bw

05 ± 0. Rate constants for the reduction of [Co(NH3)5N3]2+ by [Ru(bpy)3]2+ at different temperatures.09 318 4.0 19.5 M.9 67. RESULTS AND DISCUSSION The reactions between the ruthenium(II) complexes and excess Co(III) concentrations follow first order kinetics in the reductants. Plots of ks against the concentration of the oxidant were linear for each reaction (Figure 1).2 104 [Co(III).A∞) against time.54 ± 0. K 2.61 3.5 M with HCl/LiCl. s-1 k2.3 54.42 10. were obtained from linear regression plots of ln(At .3 12.8 35.0 6.2 5.41 2. K 104 [Co(III). M-1s-1 T. Each reaction was studied under pseudo first-order conditions with the concentrations of the Co(III) complexes in large excess. This observation is consistent with the rate law: d [Ru(II)] = k s [Ru(II)] = k2 [Co(III)][Ru(II)] dt where ks = k2[Co(III)] − (1) (2) The reactions can generally be represented by the following equations: Ru(II) + Co(NH3)5X2+ Co(NH3)5X+ ] [H   → +  → Ru(III) + Co(NH3)5X+ (3) (4) Co2+ + 5NH4+ + X- Table 1.8 6.2 15.4 19.85 4. Kinetics.7 k2. Ethiop.8 6.2 4.9 2.8 6.03 328 113. [Ru(bpy)32+] = 2. All reactions were followed with a Shimadzu UV-2501 PC UV/vis spectrophotometer equipped with a TCC peltier temperature controller for the cell compartment.8 5.2 23.0 4.03 313 32. for the reactions were found to increase with increasing concentrations of the oxidants at constant temperature (Tables 1-3).0 3.71 4. respectively. M 104 ks.8 4.3 ± 0.1 45. 2006.2 4.5 2. t. M-1s-1 303 47. The pseudo first-order rate constants.2 4. [Co(NH3)5Cl]Cl2 and [Co(NH3)5N3]Cl2 were prepared and characterised following established procedures [1]. indicating that each reaction is also first order with respect to the Co(III) oxidant and second order overall.0 4.33 3.46 3.22 ± 0. M 104 ks.0 9. Absorbance changes were monitored at 454 and 477 nm for reactions involving [Ru(bipy)3]2+ and [Ru(terpy)(bipy)Cl]+.0 7. 20(2) .0 14.0 6.8 6.0 x 10-5 M.2 3.7 2.05 308 74.89 17. Soc.8 4. ks.1 4.0 3. s-1 2.0 3. I = 0. The pseudo first-order rate constants.8 8.228 Olayinka A.82 12.0 29. [Ru(bipy)3]Cl2 was obtained from Aldrich Chemicals and used without further purification. The ionic strength was kept at 0. Chem.9 3.66 6.57 6.0 22.0 4. T.0 10.8 22.0 2.51 ± 0. The second-order rate constants obtained from slopes of such plots for the different reactions at different temperatures are also shown in Tables 1 to 3.0 44.0 28. Oyetunji et al.8 15. ks.6 36.3 Bull.17 323 4.88 ± 0.

09 ± 0.9 4.8 12. K 104 [Co(III). K 104 [Co(III).82 4.1 4. k(Cl-) ≈ k(N3-) ≈ k(SCN-) [12.0 3.40 ± 0.60 5.61 4. M-1s-1 298 1. Soc.0 18. Rate constants for the reduction of [Co(NH3)5N3]2+ by [Ru(terpy)(bipy)Cl]2+ at different temperatures.0 3.92 2.1 12.0 3.8 4.0 4.4 k2.0 3.74 ± 0.0 4. k(N3-) is slightly less than k(Cl-) which Bull.8 7.05 6.75 to 15. s-1 2. (M-1 s-1) of 1.10 2.06 323 5. M-1s-1 T. the chloro.01 4.06 5.and azido-pentaamminecobalt(III) complexes are reduced by [Ru(terpy)(bpy)Cl]+ under similar conditions with electron transfer rate constants.0 14.0 3.0 4.08 6.40 and 1.0 3.4 k2.5 M.30 2. M 104 ks.0 4. In the reactivity pattern of the pentaamminecobalt(III) complexes.45 9.0 11.98 5. respectively.01 318 1.53 6.8 8.0 104 ks.03 ± 0.2 4.7 6.2 16.0) x 10-4 M-1 s-1 [11].8 19.8 6. M 2.0 21.0 24.5 6.61 4. I = 0.02 308 1.9 4.02 313 1.01 303 1.8 6. Ethiop. 13].03 313 3.5 3.0 5. I = 0.2 4. M-1s-1 T.96 8.64 3.01 4.57 ± 0. Rate constants for the reduction of [Co(NH3)5Cl]2+ by [Ru(terpy)(bipy)Cl]2+ at different temperatures.9 2. s-1 2.90 3.52 6.0 6.50 3.03 3.0 4.2 8. K 104 [Co(III). the order of reactivity for outer sphere reactions is: k(Cl-) < k(N3-) < k(SCN-) and for inner sphere.0 2.39 10.09 303 1.0 9.04 [Ru(terpy)(bpy)H2O]2+ undergoes substitution at 298 K with rate constants.81 8.0 7. ket.0 2.63 ± 0. These rate constants are about 4 orders of magnitude higher than the expected substitution rate constant for the same reductant.0 10.01 Table 3. K 104 [Co(III).02 323 2. M 104 ks.68 4.5 2.0 5.62 10.2 6.52 3.81 2.5 M.8 6. T.10 3.40 6.31 7.60 5.0 2.72 4.0 104 ks.0 15.10 6.17 6. 2006. For the [Ru(terpy)(bpy)Cl]+ complex. The fact that ket is much greater than ksub indicates outer sphere electron transfer between the ruthenium(II) reductants and cobalt(III) oxidants. M-1s-1 298 1. ksub.78 ± 0.2 10.0 4.30 3.0 2.52 k2.8 15.4 4.8 6.2 4.03.8 25.6 6. We do not expect any significant difference in ksub for [Ru(terpy)(bpy)Cl]+.Non-bridging ligand effects on the kinetics of reduction of pentaamminecobalt(III) 229 Table 2.3 6.0 15.0 3.2 4. of (0.21 3. Chem.31 5.0 4. s-1 2.8 6.5 4. T.0 2.46 6.0 8. M 2.0 8. In the present study.2 k2.07 ± 0.0 32.2 4.81 8.14 ± 0.24 ± 0.8 6.2 4.2 4.0 4.05 308 2.33 ± 0.41 ± 0. s-1 2.32 4. 20(2) .04 318 4.2 12.

all at 308 K. 16]. If the mechanisms of electron transfer were substitution controlled as observed in many inner sphere reactions [15. Ethiop. the magnitude of the increase seems to be reduced by the steric effects of the non-bridging π-acceptor ligands. 120 a 100 80 -1 10 k s . Although Cl. 6. 2006. It becomes obvious that the effect of the non-bridging ligands on the ruthenium(II) complexes is very small on the electron transfer rate constants as compared to the substitution rate constants. In previous studies [1. Chem. M Figure 1. Our proposed outer sphere reduction by [Ru(terpy)(bpy)Cl]+ falls in line with what was observed in these earlier studies. Soc. the order of reactivity is [Ru(NH3)5H2O]2+ < [Ru(terpy)(bpy)Cl]+ < [Ru(bipy)(bquin)Cl2] for reductions of both cobalt(III) complexes. but other mechanistic criteria favour an outer sphere electron transfer mechanism. s 60 4 40 20 b c 0 0 2 4 4 6 8 10 [CoIII].230 Olayinka A.ligands on the ruthenium(II) reductants did not change the mechanism of electron transfer even though these ligands are expected to make the complexes more labile. [Ru(NH3)5H2O]2+. 20(2) . where the nature of the nonbridging ligands alters the substitution rate constants by up to five orders of magnitude (Table 4). then a more significant difference would be expected in the rate constants as the π-acceptor spectator ligands are introduced into the coordination sphere of the ruthenium(II) reductants. it has been suggested that the two cobalt(III) complexes are reduced by [Ru(NH3)6]2+. Bull. When this complex is compared with other ones. The presence of the H2O and Cl. Similar effects have been observed in the substitution reactions of ruthenium(II) complexes. 14]. may suggest an inner sphere mechanism. Plot of ks against Co(III) concentration for the reduction of (a) [Co(NH3)5N3]2+ by Ru(bipy)32+. (b) [Co(NH3)5Cl]2+ by Ru(terpy)(bipy)Cl+ and (c) [Co(NH3)5N3]2+ by Ru(terpy)(bipy)Cl+.as a potential bridging ligand increases the reactivity of the ruthenium(II) complexes. Oyetunji et al. and [Ru(bipy)(bquin)Cl2] via an outer sphere mechanism.

may be associated with the fact that the overall activation entropy obtained is a composite parameter which reflect both outer-sphere precursor association and electron transfer within the assembly [27] according to equation 5.82 0.75 – 15. This obviously cannot be a quenching rate constant.0) x 10-4 - The second order rate constants for all the reactions increased as temperature was increased. Soc. and some Co(III) complexes with quenching rate constants that vary from 107 to 109 M-1 s-1.18 8. ∆S≠ = ∆Soso + ∆Set≠ ≠ (5) ≠ Contributions to ∆S by and ∆Set can vary from one reaction to another thereby affecting ∆S≠. The positive ∆H≠ and negative ∆S≠ values obtained for reductions by [Ru(terpy)(bipy)Cl]+ are similar to earlier reports (Table 3) and also in agreement with what is expected for reactions involving ions of similar charges [27]. Similar observations have been reported in some earlier outer-sphere reactions [22.89 1. 19. 18] to be excited to the triplet state CT[Ru(bipy)3]2+ and then quenched to the ground state before oxidation to [Ru(bipy)3]3+. For example. a plot of ∆H≠ against ∆S≠ values was found to be linear as shown in Figure 3. 3 Table 4.31 M-1 s-1. The process of excitation and quenching was observed to be very rapid. Fe2+. 20(2) . 20 11 14 This work This work 0. [Co(NH3)5N3]2+ reacts at the same temperature with [Ru(bipy)3]2+ with a rate constant of 4.36 (0. 28]. Complex ksub M-1 s-1 2+ ket (M-1 s-1) for reduction of [Co(NH3)5X]2+ X = Cl X = N3 260 0. Eyring plots were drawn (Figure 2) and activation parameters ∆H≠ and ∆S≠ were respectively obtained from the slopes and intercepts of the plots. k and l) representing this study all fall within this linear plot. 2006. Substitution and electron-transfer rate constants for reactions of some ruthenium(II) complexes at 298 K.61 1.Non-bridging ligand effects on the kinetics of reduction of pentaamminecobalt(III) 231 [Ru(bipy)3]2+ has been shown in earlier studies [17. In this study.02 – 0. The positive ∆S≠ obtained in the reduction of the azidocobalt(III) complex by [Ru(bipy)3]2+ as compared to the other two reactions involving [Ru(terpy)(bipy)Cl]+ as a reductant.79 1. The three points (j. at 293 K 3 CT[Ru(bipy)3]2+ is quenched by Fe3+. 7 6. ∆Soso Bull.03 7. This further supports outer-sphere mechanism for the reduction of the cobalt(III) complexes by the ruthenium(II) reductants.22 Reference [Ru(NH3)6]2+ [Ru(NH3)5H2O] [Ru(terpy)(bipy)H2O]2+ [Ru(bipy)(bquin)Cl2] [Ru(terpy)(bipy)Cl] [Ru(bipy)3]2+ + 1.40 1. Tl3+. From this table. Chem. Ethiop. These ∆H≠ and ∆S≠ values are compared with values obtained for some typical outer-sphere reactions shown in Table 5. From Tables 1-3.

Chem. Reactions represented by ‘a’ to ‘l’ are indicated in Table 5.232 0 Olayinka A. Plot of ∆S≠ against ∆H≠ for some typical outer-sphere reactions.2 3. (b) [Co(NH3)5Cl]2+ by Ru(terpy)(bipy)Cl+ and (c) [Co(NH3)5N3]2+ by Ru(terpy)(bipy)Cl+.3 -1 3. 2006.1 3 3. Ethiop. K Figure 2.4 10 (1/T). Soc. 20(2) . -1 -2 ln(k2/T) -3 a -4 -5 b -6 c -7 3 3. Bull. Eyring plots for the reduction of (a) [Co(NH3)5N3]2+ by Ru(bipy)32+. Oyetunji et al. Figure 3.

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