Tuning Reactivity of Platinum(II) Complexes

Table S6.3: Average observed rate constants, kobs(2 nd ), at 298.15 K, for the reactions of
Pt3 with a series of nucleophiles at different concentrations.
[NU]/ M kobs(2 nd ),s -1
k obs(1 st ) in s -1
(a)
TU DMTU TMTU SCN ¯ I ¯
0.00125 2.253 x 10 -5 9.510 x 10 -6 1.782 x 10 -6 1.820 x10 -5 1.577 x10 -6
0.00225 4.595 x 10 -5 1.632 x 10 -5 3.164 x 10 -6 3.330 x 10 -5 2.825 x 10 -6
0.00338 6.983 x 10 -5 2.628 x 10 -5 4.911 x 10 -6 5.170 x 10 -5 4.025 x 10 -6
0.0045 9.253 x 10 -5 3.384 x 10 -5 6.401 x 10 -6 6.580 x 10 -5 5.200 x 10 -6
0.00653 1.326 x 10 -4 4.899 x 10 -5 9.513 x 10 -6 9.460 x 10 -5 7.873 x 10 -6
0.3
0.2
0.1
0.0
SCN
TU
DMTU
TMTU
0.000 0.002 0.004 0.006 0.008 0.010 0.012
[NU]/dm -3
k obs(1 st ) in s -1
35
(b)
0.14
0.12
0.10
0.08
0.06
0.04
0.02
0.00
I
Br
0.000 0.002 0.004 0.006 0.008 0.010 0.012
[NU]/dm -3
Figure S6.1: Concentration dependence of kobs(1 st ) for the simultaneous substitution of
aqua ligands in Pt3 by (a) thiourea nucleophiles and (b) ionic nucleophiles at
pH = 2.0, T = 298.15 K, I = 0.10 M (0.01 M HClO4, adjusted with NaClO4).