0.0
31.3
-48.0
TS C-G
23.8
23.2
3 A
Pt
N
N
N
Me
NH 2
NH 2
C
TS C-F
G
31.8
TS 3 A-B
-19.7
TS F-G
-26.6
F
MECP
C- 3 C
23.3
3 C
A
TS 3 C-A
13.0
h ν
5.7
-17.6
3 O 2
Pt
N
N
N
Me
NH 2
NH 2
Pt
N
N
N
Me
NH 2
NH 2
O
O
Pt
N
N
N
Me
NH 2
NH 2
O
O
Pt
N
N
N
O
NH 2
NH 2
Me
O
Pt
N
N
N
O
NH 2
NH 2
Me
O
Pt
N
N
N
Me
NH 2
NH 2
O
O
Pt
N
N
N
O
NH 2
NH 2
Me
O
Pt
N
N
N
O
NH 2
NH 2
Me
O
Pt
N
N
N
O
NH 2
NH 2
Me
O
- 3 O 2
23.9
B
Pt
N
N
N
Me
NH 2
NH 2
O
O
Fig. 15 Gibbs energy profile for the full scenario of the O 2 insertion into the Pt(II)–Me bond upon
irradiation. Energies are Gibbs energies in solution, in kcal/mol. MECP stands for minimum energy
crossing point
23.2
3 A
Pt
N
N
N
Me
NH 2
NH 2
31.8
TS 3 A-B
3 O 2
36.1
TS 3 A-D
0.0
C
Pt
N
N
N
Me
NH 2
NH 2
O
O
1.5
D
6.3
B
Pt
N
N
N
Me
NH 2
NH 2
O
O
Pt
N
N
N
O
NH 2
NH 2
Me
O
+
Pt
N
N
N
Me
NH 2
NH 2
O
O
Fig. 16 Gibbs energy profile for the alternative pathways for the reaction between
3
A and
3
O 2 .
Energies relative to intermediate C in kcal/mol
Computational Modeling of Selected Photoactivated Processes
149