Mechanisms for Nickel(0)/N-Heterocyclic
Carbene-Catalyzed Intramolecular Alkene Hydroacylation:
Insights from A DFT Study
Qingxi Meng[a], *, Fen Wang[b]
[a] College of Chemistry and Material Science, Shandong Agricultural University,
Taian, Shandong, 271018, People’s Republic of China.
[b] Department of Chemistry, Taishan University, Taian, Shandong, 271021, People’s
Republic of China.
Figure S1. Intermediates and transition state of the oxidative addition in nickel(0)/ N-heterocyclic
carbene-catalyzed intramolecular alkene hydroacylation. Bond distances were in angstrom (Å),
and bond angles were in degree (°).
Figure S2. Intermediates and transition states of the reaction pathway I in nickel(0)/
N-heterocyclic carbene-catalyzed intramolecular alkene hydroacylation. Bond distances were in
angstrom (Å), and bond angles were in degree (°).
Figure S3. Intermediates and transition states of the reaction pathway II in nickel(0)/
N-heterocyclic carbene-catalyzed intramolecular alkene hydroacylation. Bond distances were in
angstrom (Å), and bond angles were in degree (°).
Figure S4. Intermediates and transition states of the reaction pathway III in nickel(0)/
N-heterocyclic carbene-catalyzed intramolecular alkene hydroacylation. Bond distances were in
angstrom (Å), and bond angles were in degree (°).
Figure S5. Intermediates and transition states of the reaction pathway IV in nickel(0)/
N-heterocyclic carbene-catalyzed intramolecular alkene hydroacylation. Bond distances were in
angstrom (Å), and bond angles were in degree (°).
Table S1. Relative free energies ΔG (kJ·mol-1), relative enthalpies ΔH (kJ·mol-1), relative energies
including zero point vibrational energy correlation ΔE (kJ·mol-1) and absolute entropies S
(kJ·mol-1·K-1), and the first two frequencies (cm-1) for the stationary points in nickel(0)/
N-heterocyclic carbene-catalyzed intramolecular alkene hydroacylation.
Table S2. Selected stabilization interaction energies E(2) for TS1-5 (kJ/mol).
Figure S1. Intermediates and transition state of the oxidative addition in nickel(0)/
N-heterocyclic carbene-catalyzed intramolecular alkene hydroacylation. Bond distances
were in angstrom (Å), and bond angles were in degree (°).
Figure S2. Intermediates and transition states of the reaction pathway I in nickel(0)/
N-heterocyclic carbene-catalyzed intramolecular alkene hydroacylation. Bond distances
were in angstrom (Å), and bond angles were in degree (°).
Figure S3. Intermediates and transition states of the reaction pathway II in nickel(0)/
N-heterocyclic carbene-catalyzed intramolecular alkene hydroacylation. Bond distances
were in angstrom (Å), and bond angles were in degree (°).
Figure S4. Intermediates and transition states of the reaction pathway III in nickel(0)/
N-heterocyclic carbene-catalyzed intramolecular alkene hydroacylation. Bond distances
were in angstrom (Å), and bond angles were in degree (°).
Figure S5. Intermediates and transition states of the reaction pathway IV in nickel(0)/
N-heterocyclic carbene-catalyzed intramolecular alkene hydroacylation. Bond distances
were in angstrom (Å), and bond angles were in degree (°).
Table S1. Relative free energies ΔG (kJ·mol-1), relative enthalpies ΔH (kJ·mol-1), relative
energies including zero point vibrational energy correlation ΔE (kJ·mol-1) and absolute entropies
S (kJ·mol-1·K-1), and the first two frequencies (cm-1) for the stationary points in nickel(0)/
N-heterocyclic carbene-catalyzed intramolecular alkene hydroacylation.
stationary
points
ΔG
ΔH
ΔE
S
2
TS2-3a
TS2-3b
3a
0.0
32.2
-6.1
89.9
89.8
-38.7
0.0
28.4
-0.3
85.7
85.7
-37.0
0.0
30.4
-1.1
87.3
87.3
-37.0
0.734
0.722
0.740
0.720
0.721
0.740
3b
TS3a-4a
TS3b-4b
4a
4b
-3.4
26.0
17.0
-87.4
-105.3
-5.0
22.5
12.7
-79.1
-107.0
-4.1
23.9
15.1
-79.3
-104.8
0.729
0.723
0.720
0.762
0.729
TS1-5
5
TS5-6
6
TS6-4a
63.4
-34.0
230.9
-35.0
16.7
54.3
-40.1
225.3
-37.1
17.4
58.7
-36.3
228.2
-34.8
18.9
7
TS7-8
8
TS8-9
9
-110.2
61.4
-2.1
45.9
-186.6
-8.6
-67.3
-13.7
-102.4
-166.2
1
TS1-2
frequencies
υ1
υ2
25.7
203.5i
23.0
701.8i
697.4i
14.9
20.6
37.1
27.0
29.7
22.6
21.9
31.4
33.7
195.7i
331.4i
13.5
13.9
24.3
21.5
17.0
34.5
0.704
0.714
0.715
0.728
0.737
284.3i
18.1
801.0i
22.8
25.2
19.9
17.7
826.7i
28.5
16.8
-182.2
-6.0
-66.7
-13.9
1.192
1.214
1.230
1.249
17.2
160.3i
9.5
849.4i
-165.7
1.235
7.9
20.1
15.7
19.4
7.1
14.9
Table S2. Selected stabilization interaction energies E(2)
for TS1-5 (kJ/mol)
E(2)
donor NBO
acceptor NBO
BD Ni-C1
BD Ni-C7
LP(3) O1
LP(4) Ni
BD C2-O1
BD C2-C6
BD C6-C7
BD* Ni-C7
BD* Ni-C1
LP*(5) Ni
80.0
185.4
248.9
π* C1-N1
LP*(5) Ni
LP*(7) Ni
LP*(7) Ni
42.3
78.2
60.9
77.7