Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
Pseudo-rotation mechanism for fast olefin exchange and substitution
processes at orthometalated C,N – complexes of platinum(II)
Stefanus Ottoa, Pavel V. Samuleev,a Vladimir A. Polyakovb, Alexander D. Ryabovc and Lars
I. Eldinga
a
Inorganic Chemistry, Chemical Center, Lund University, P. O. Box 124, SE-221 00 Lund,
Sweden, E-mail: LarsI.Elding@inorg.lu.se
b
D.I. Mendeleev Moscow University of Chemical Technology, Miusskaya sq. 9, 125820,
Moscow, Russia
c
Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA 15213, USA
Synopsis
Fast olefin exchange and substitution reactions at cycloplatinated C,N complexes are proposed to
take place as concerted substitution/isomerization processes via pseudorotation in a labile 5coordinated intermediate, involving initial attack on the labile coordination position trans to the
-bonded aryl; bridge-cleavage reactions of analogous dinuclear complexes occur similarly, but
are much slower because of ground-state stabilization and steric hindrance.
Table S1. Observed pseudo first-order rate constants (x104) for the bridge splitting reaction of
[Pt(-Cl)(Me2NCH2C6H4)]2 (1) with ethene at 291.4, 303 and 323 K in chloroform-d1 ([1] = 14.3
mM).
Table S2. Observed pseudo first-order rate constants (x104) for the bridge splitting reaction of
[Pt(-Cl)(Me2NCH2C6H4)]2 (1) with cyclooctene at 288.2, 298.2, 308.2 and 318.2 K in
chloroform at 330 nm ([1] = 0.125 mM).
Table S3. Observed pseudo first-order rate constants (x104) for the bridge splitting reaction of
[Pt(-Cl)(Me2NCH2C6H4)]2 (1) with allylalcohol at 288.2, 293.2, 298.2, 303.2, 308.2, 313.2 and
318.2 K in chloroform at 300 nm ([1] = 0.25 mM).
Table S4. Observed pseudo first-order rate constants for ethene substitution by cyclooctene from
[Pt(Me2NCH2C6H4)Cl(C2H4)] (3a) at 248.2, 258.2, 268.2, 278.2, 288.2 and 298.2 K in
chloroform at 270 nm ([3a] = 0.5 mM).
1
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
Table S5. Observed pseudo first-order rate constants for ethene substitution by allylalcohol from
[Pt(Me2NCH2C6H4)Cl(C2H4)] (3a) at 258.2, 268.2, 278.2, 288.2 and 298.2 K in chloroform at
265 nm ([3a] = 0.50 mM).
Table S6. Observed pseudo first-order rate constants for cyclooctene substitution by allylalcohol
from [Pt(Me2NCH2C6H4)Cl(cot)] (3b) at 248.2, 258.2, 268.2, 278.2, 288.2 and 298.2 K in
chloroform at 300 nm ([3b] = 0.50 mM).
Table S7. Observed rate constants for cyclooctene exchange on [Pt(Me2NCH2C6H4)Cl(cot)]
(31.6 mmol dm-3) in chloroform-d1 at 283.2, 288.2, 293.2, 298.2 and 303.2 K for different [cot].
Table S8. Observed rate constants for cyclooctene exchange on [Pt(Me2NCH2C6H4)Cl(cot)] in
chloroform-d1 at 293.2 K for different platinum concenttrations.
Table S9. 13C NMR data for complexes 1-4 obtained in CDCl3 (, J are in Hz; coupling to
195
Pt
is indicated in parentheses).
Figure S1. kobs vs. [Pt(Me2NCH2C6H4)Cl(cot)] concentration for cyclooctene exchange at
[Pt(Me2NCH2C6H4)Cl(cot)] in chloroform-d1 at 293.2 K.
Table S1. Observed pseudo first-order rate constants (104) for the bridge splitting reaction of
[Pt(-Cl)(Me2NCH2C6H4)]2 (1) with ethene at 291.4, 303 and 323 K in chloroform-d1 ([1] = 14.3
mmol dm-3).
[ethene] /
mmol dm-3
50
59
102
150
204
291.4 K
103k2 /
mol-1 dm3 s-1
1.20(10)
0.83
0.88
1.30
2.17
2.57
H2 = 54  14 kJ mol-1
[ethene] /
mmol dm-3
30
55
100
151
201
303 K
0.55
1.00
1.83
2.67
3.50
[ethene] /
mmol dm-3
5
13
16
20
51
75
85
1.72(2)
323 K
0.58
1.38
1.67
2.40
4.83
7.50
9.50
10.5(5)
S2 = -118  42 J K-1 mol-1
2
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
Table S2. Observed pseudo first-order rate constants (104) for the bridge splitting reaction of
[Pt(-Cl)(Me2NCH2C6H4)]2 (1) with cyclooctene at 288.2, 298.2, 308.2 and 318.2 K in
chloroform at 330 nm ([1] = 0.125 mmol dm-3).
[cot] / mmol dm-3
25
50
75
100
150
200
103k2 / mol-1 dm3 s-1
H2 = 52.9  0.7 kJ mol-1
288.2 K
0.4382(9)
0.569(2)
1.093(18)
0.554(9)
298.2 K
0.27542(18)
0.5415(6)
0.8695(7)
1.1859(19)
1.838(4)
2.467(5)
1.215(15)
308.2 K
0.5612(9)
1.067(4)
1.844(4)
2.430(9)
3.769(10)
5.362(18)
2.57(6)
318.2 K
1.152(12)
2.188(12)
3.788(5)
5.085(8)
7.63(2)
9.68(5)
4.94(7)
S2 = -123  4 J K-1 mol-1
Table S3. Observed pseudo first-order rate constants (104) for the bridge splitting reaction of
[Pt(-Cl)(Me2NCH2C6H4)]2 (1) with allylalcohol at 288.2, 293.2, 298.2; 308.2, 313.2 and 318.2
K in chloroform at 300 nm ([1] = 0.25 mmol dm-3).
[allylalcohol] / mmol dm-3
25
50
75
100
150
200
103k2 / mol-1 dm3 s-1
H2 = 52.5  0.8 kJ mol-1
288.2 K
0.7846(5)
1.550(2)
2.339(6)
3.021(8)
1.45(3)
298.2 K
0.8812(3)
1.5844(8)
2.4280(13)
3.168(5)
4.779(5)
6.285(6)
3.11(3)
308.2 K
1.620(2)
3.327(5)
5.107(6)
6.654(14)
9.972(7)
13.206(11)
6.61(5)
318.2 K
3.762(12)
6.500(12)
10.15(5)
13.08(8)
19.42(2)
25.65(5)
12.59(13)
S2 = -117  3 J K-1 mol-1
3
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
Table S4. Observed pseudo first-order rate constants for ethene substitution by cyclooctene from
[Pt(Me2NCH2C6H4)Cl(C2H4)] (3a) at 248.2, 258.2, 268.2, 278.2, 288.2 and 298.2 K in
chloroform at 270 nm ([3a] = 0.5 mmol dm-3).
[cot] / mmol dm-3
5
10
25
50
75
100
10-3k2 /mol-1 dm3 s-1
248.2 K
4.36(2)
7.66(3)
14.14(7)
22.6(1)
29.6(1)
37.6(2)
0.340(15)
H2 = 19.3  0.5 kJ mol-1
258.2 K
6.71(3)
10.28(5)
19.0(1)
32.3(1)
46.0(2)
58.8(3)
0.546(7)
268.2 K
9.92(5)
14.2(1)
26.7(1)
44.7(2)
66.8(4)
81.3(7)
0.763(21)
278.2 K
13.0(1)
18.7(1)
35.8(2)
60.4(2)
87(1)
116(1)
1.071(13)
288.2 K
16.7(1)
24.9(1)
47.0(2)
85.7(4)
122(1)
166(1)
1.556(25)
298.2 K
21.0(1)
33.3(2)
61.5(3)
109(1)
163(2)
205(2)
1.948(31)
S2 = -117  2 J K-1 mol-1
Table S5. Observed pseudo first-order rate constants for ethene substitution by allylalcohol from
[Pt(Me2NCH2C6H4)Cl(C2H4)] (3a) at 258.2, 268.2, 278.2, 288.2 and 298.2 K in chloroform at
265 nm ([3a] = 0.50 mmol dm-3).
[allylalcohol] / mmol dm-3
5
10
15
20
25
40
10-3k2 /mol-1 dm3 s-1
258.2 K
29.0(1)
49.2(2)
70.2(5)
91(1)
180(2)
4.34(5)
H2 = 13.7  0.7 kJ mol-1
268.2 K
36.6(2)
64.7(3)
96.4(4)
124(1)
155(1)
250(2)
6.10(7)
278.2 K
45.8(2)
84.5(5)
126(1)
160(1)
200(1)
307(3)
7.5(1)
288.2 K
59.7(2)
103.4(6)
161(1)
216(2)
251(2)
383(5)
9.3(3)
298.2 K
66.9(4)
120(1)
196(2)
260(6)
303(3)
12.2(6)
S2 = -121  2 J K-1 mol-1
4
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
Table S6. Observed pseudo first-order rate constants for cyclooctene substitution by allylalcohol
from [Pt(Me2NCH2C6H4)Cl(cot)] (3b) at 248.2, 258.2, 268.2, 278.2, 288.2 and 298.2 K in
chloroform at 300 nm ([3b] = 0.50 mmol dm-3).
[Allylalcohol] / mmol dm-3
5
10
15
20
30
40
10-3k2 / mol-1 dm3 s-1
248.2 K
258.2 K
9.55(3)
18.1(1)
28.0(2)
39.0(2)
58.4(3)
81.3(4)
2.05(4)
12.70(6)
19.4(1)
27.4(1)
40.7(2)
54.1(2)
1.38(2)
H2 = 16.8  0.4 kJ mol-1
268.2 K
14.73(4)
29.0(1)
44.1(1)
56.1(2)
87.6(4)
113(1)
2.83(5)
278.2 K
20.5(1)
40.5(1)
59.4(2)
77.4(4)
117(1)
150(1)
3.72(6)
288.2 K
29.2(1)
54.7(2)
77.3(4)
106(1)
156(1)
212(3)
5.21(7)
298.2 K
67.7(1)
63.4(5)
93(1)
125(1)
174(2)
256(3)
6.5(4)
S2 = -115  2 J K-1 mol-1
Table S7. Observed rate constants for cyclooctene exchange on [Pt(Me2NCH2C6H4)Cl(cot)]
(31.6 mmol dm-3) in chloroform-d1 at 283.2, 288.2, 293.2, 298.2 and 303.2 K for different [cot].
[cot] / mmol dm-3
283.2 K
288.2 K
293.2 K
298.2 K
303.2 K
21.9
4.8
7.00
7.9
9.5
11.1
43.6
12.0
12.7
15.5
19.3
20.6
65.2
17.4
19.6
24.1
26.3
31.3
86.7
22.5
25.3
30.7
33.9
39.6
108.1
27.2
31.7
39.6
46.8
53.8
10-3kex /mol-1 dm3 s-1
0.257(2)
0.288(1)
0.364(1)
0.414(5)
0.484(4)
H2 = 20.8  0.3 kJ mol-1
S2 = -124.9  1.6 J K-1 mol-1
5
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
Table S8. Observed rate constants for cyclooctene exchange on [Pt(Me2NCH2C6H4)Cl(cot)] in
chloroform-d1 at 293.2 K for different platinum concenttrations.
[cot] / mmol dm-3
[Pt(Me2NCH2C6H4)Cl(cot)] / mmol dm-3
kobs / s-1
65.2
15.4
5.76
65.2
31.6
11.66
65.2
57.5
21.47
10-3kex /mol-1 dm3 s-1
0.368(1)
25
kobs / s
-1
20
15
10
5
0
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
-3
[Pt(Me2NCH2C6H4)Cl(cot)] / mol dm
Figure S1. kobs vs. [Pt(Me2NCH2C6H4)Cl(cot)] concentration for cyclooctene exchange at
[Pt(Me2NCH2C6H4)Cl(cot)] in chloroform-d1 at 293.2 K.
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Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
Table S9. 13C NMR data for complexes 1-4 obtained in CDCl3 (, J are in Hz; coupling to 195Pt is indicated in parentheses).
Complex
C1
C2
C3
C4
C5
C6
C7
C8
1 ab-gh
146.54
122.11
120.62
131.05
124.05
124.87
75.24
54.15
1 ab-hg
146.33
122.11
120.55
131.90
124.05
125.02
75.50
53.72
2
145.21(820) 143.33(72)
119.16(34)
123.19(14)
119.16(34)
143.33(72)
a
57.7(12)
3a
147.45(846) 132.28(89)
125.08(10)
126.3(51)
121.85(20)
128.6(52)
72.32 (40)
57.7(12)
Ethene
70.19(191)
3b
87.47(191)
3c
93.62(198)
4bb
a
146.60
129.42
121.19(35)
122.48
124.63(70)
130.66(38)
74.39
51.00
signal is obscured by the solvent; b P-Ph: 137.10(80) 1’C, 134.70(20) 2’,6’, 127.30 3’,5’.
7