Supporting Information

Substitution reactions of dinuclear platinum(II) complexes with some nitrogen nucleophiles

Enisa Selimovića, Tanja Soldatovića, Jovana Bogojeskib and Živadin D. Bugarčićb,*

aDepartment of Chemical-Technological Sciences, State University of Novi Pazar,

Vuka Karadžića bb, 36300 Novi Pazar, Serbia

bDepartment of Chemistry, Faculty of Science, University of Kragujevac,

R. Domanovića 12, P. O. Box 60, 34000 Kragujevac, Serbia

* Corresponding author: Prof. Dr. Živadin D. Bugarčić

Department of Chemistry,Faculty of Science,

University of Kragujevac

R. Domanovića 12, 34000 Kragujevac, Serbia

Phone: +381(0)34300262

Fax: +381(0)34335040

e-mail:

Table S1

Observed pseudo-first order rate constants as a function of ligand concentration for the substitution reactions of diaqua Pt1 complex in 0.01 MNaClO4(pH = 2.5) at 310 K.

LIGANDS / λ [nm] / 103CL [M] / 103kobsd1 [s-1] / 104kobsd2 [s-1]
1,2,4-Triazole / 1 / 6.14(3)a / 7.11(3)
2 / 8.52(3) / 8.21(3)
315 / 3 / 13.03(4) / 10.00(3)
4 / 17.85(3) / 12.60(4)
5 / 23.80(3) / 15.40(3)
His / 1 / 1.87(2) / 2.29(4)
2 / 3.24(2) / 2.58(3)
327 / 3 / 4.83(3) / 2.93(3)
4 / 5.88(4) / 3.36(3)
5 / 7.92(3) / 3.99(4)
5’- IMP / 1 / 0.40(3) / 0.89(3)
2 / 1.74(3) / 1.24(4)
3 / 1.85(3) / 1.45(3)
327 / 4 / 1.89(3) / 1.66(3)
5 / 2.12(3) / 2.04(3)

aNumber of runs in parenthesis.

Table S2

Observed pseudo-first order rate constants as a function of ligand concentration for the substitution reactions of diaquaPt1 complex in 0.01 MNaClO4(pH = 2.5) at 288and 298 K.

LIGANDS / λ [nm] / 103CL [M] / 103kobsd1 [s-1] / 104kobsd2 [s-1]
1,2,4-Triazole
(288 K) / 1 / 1.48(2) / 0.91(2)
2 / 2.10(3) / 1.11(3)
315 / 3 / 3.02(4) / -
4 / - / 1.42(4)
5 / 4.25(3) / 1.55(3)
1,2,4-Triazole
(298 K) / 1 / 1.50(2) / 1.34(2)
2 / 2.52(4) / 2.20(3)
315 / 3 / 3.67(3) / 3.10(3)
4 / 4.51(3) / 3.96(3)
5 / 6.28(3) / 4.92(4)

Table S3

Observed pseudo-first order rate constants as a function of ligand concentration for the substitution reactions of diaquaPt2 complex in 0.01 MNaClO4(pH = 2.5) at 310 K.

LIGANDS / λ [nm] / 103CL [M] / 103kobsd1 [s-1] / 104kobsd2 [s-1]
1,2,4-Triazole / 1 / 1.75(3) / 1.89(3)
2 / 3.06(3) / 2.49(3)
325 / 3 / 4.72(4) / 3.58(3)
4 / 6.51(3) / 4.15(4)
5 / 8.01(3) / 5.57(3)
His / 1 / 0.90(3) / 0.99(4)
2 / 2.17(3) / 1.30(3)
329 / 3 / 2.80(2) / 1.72(3)
4 / 3.86(3) / 2.26(3)
5 / 4.60(3) / 2.53(3)
5’- IMP / 1 / 0.09(4) / 0.82(3)
2 / 0.41(3) / 1.08(3)
3 / 0.49(3) / 1.36(3)
336 / 4 / 0.65(3) / 1.91(3)
5 / 0.78(2) / 2.26(4)

Table S4

Observed pseudo-first order rate constants as a function of ligand concentration for the substitution reactions of diaquaPt3 complex in 0.01 MNaClO4(pH = 2.5) at 310 K.

LIGANDS / λ [nm] / 103CL [M] / 103kobsd1 [s-1] / 104kobsd2 [s-1]
1,2,4-Triazole / 1 / 2.28(3) / 1.52(4)
2 / 3.58(3) / 2.24(4)
240 / 3 / 4.40(3) / 2.74(3)
4 / 5.48(3) / 2.94(3)
5 / 6.55(3) / 3.59(3)
His / 1 / 0.29(4) / 0.61(3)
2 / 0.41(3) / 0.74(4)
263 / 3 / 0.51(3) / 0.87(3)
4 / 0.67(3) / 1.09(3)
5 / 0.84(3) / 1.31(3)
5’- IMP / 1 / 0.16(4) / 0.46(3)
2 / 0.17(4) / 0.66(3)
3 / 0.19(3) / 0.72(4)
351 / 4 / 0.19(3) / 0.76(4)
5 / 0.21(3) / 0.88(3)

Table S5

Observed pseudo-first order rate constants as a function of ligand concentration for the substitution reactions of dichloro Pt1 complex in 25 mMHepes buffer (pH = 7.2) in addition of 20 mM NaCl at 310 K.

LIGANDS / λ [nm] / 103CL [M] / 103kobsd1 [s-1] / 104kobsd2 [s-1]
1,2,4-Triazole / 1 / 2.68(3) / 0.38(3)
2 / 3.50(3) / 0.48(4)
311 / 3 / 4.48(3) / 0.63(3)
4 / 5.05(2) / 0.81(3)
5 / 5.80(3) / 1.06(3)
His / 1 / 0.34(3) / 0.32(3)
2 / 0.48(3) / 0.40(3)
328 / 3 / 0.55(3) / 0.56(3)
4 / 0.67(2) / 0.65(2)
5 / 0.75(2) / 0.81(2)
5’- IMP / 1 / 0.06(3) / 0.12(3)
2 / 0.11(3) / 0.21(3)
328 / 3 / 0.16(3) / 0.25(3)
4 / 0.18(3) / 0.35(3)
5 / 0.24(3) / 0.39(4)

Table S6

Observed pseudo-first order rate constants as a function of ligand concentration for the substitution reactions of dichloro Pt1 complex in 25 mM Hepes buffer (pH = 7.2) in addition of 20 mMNaCl at288 K and 298 K.

LIGANDS / λ [nm] / 103CL [M] / 103kobsd1 [s-1] / 104kobsd2 [s-1]
1,2,4-Triazole
(288 K) / 1 / 0.95(4) / 0.37(4)
2 / 1.00(3) / 0.33(3)
315 / 3 / - / -
4 / 1.24(4) / 0.28(4)
5 / 1.38(3) / 0.26(3)
1,2,4-Triazole
(298 K) / 1 / 1.53(4) / 0.46(4)
2 / 2.07(4) / 0.58(3)
315 / 3 / 2.32(3) / 0.67(3)
4 / 2.80(3) / 0.78(3)
5 / 3.30(3) / 0.94(4)

Table S7

Observed pseudo-first order rate constants as a function of ligand concentration for the substitution reactions of dichloro Pt2 complex in 25 mMHepes buffer (pH = 7.2) in addition of 20 mMNaCl at 310 K.

LIGANDS / λ [nm] / 103CL [M] / 103kobsd1 [s-1] / 104kobsd2 [s-1]
1,2,4-Triazole / 1 / 1.20(3) / 0.32(3)
2 / 1.47(4) / 0.43(3)
327 / 3 / 1.84(3) / 0.54(3)
4 / 2.17(3) / 0.64(3)
5 / 2.48(4) / 0.71(4)
His / 1 / 0.59(4) / 0.29(4)
2 / 0.66(3) / 0.34(3)
338 / 3 / 0.71(3) / 0.45(3)
4 / 0.77(4) / 0.56(3)
5 / 0.91(3) / 0.61(3)
5’- IMP / 330 / 1
2
3
4
5 / 0.07(3)
0.08(3)
0.09(3)
0.10(3)
0.11(4) / 0.24(3)
0.29(3)
0.31(3)
0.36(3)
0.39(4)

Table S8

Observed pseudo-first order rate constants as a function of ligand concentration for the substitution reactions of dichloro Pt3 complex in 25 mMHepes buffer (pH = 7.2) in addition of 20 mMNaCl at 310 K.

LIGANDS / λ [nm] / 103CL [M] / 103kobsd1 [s-1] / 104kobsd2 [s-1]
1,2,4-Triazole / 1 / 0.44(3) / 0.33(2)
2 / 0.58(3) / 0.41(3)
246 / 3 / 0.71(3) / 0.49(3)
4 / 0.90(3) / 0.58(3)
5 / 1.10(3) / 0.66(4)
His / 1 / 0.34(3) / 0.74(3)
2 / 0.36(3) / 0.82(4)
285 / 3 / 0.41(3) / 0.90(3)
4 / 0.51(2) / 0.96(3)
5 / 0.58(2) / 1.05(3)
5’- IMP / 1 / 0.04(2) / 0.19(3)
2 / 0.05(3) / 0.20(3)
3 / 0.05(3) / 0.21(4)
330 / 4 / 0.06(3) / 0.23(4)
5 / 0.07(4) / 0.23(3)

Fig. S1.Pseudo-first order rate constants plotted as a function of nucleophile concentration for the first and second substitution reactions of the dichloro Pt1, Pt2 and Pt3 complexes by 1,2,4-Triazole, His and 5’-IMP at pH = 7.2 (25 mM Heppes buffer), 20 mM NaCl and310 K.

Fig. S2.Eyringplots for the two reaction steps diaqua Pt1 complex with 1,2,4-Triazole in 0.01 MNaClO4 (pH = 2.5) at 315 nm.

Fig. S3.Eyringplots for the two reaction steps of dichloro Pt1 complex with 1,2,4-Triazole in 25 mMHepes buffer (pH = 7.2) in addition of 20 mM NaCl at311 nm.