Table 1: Total Energies, Hartrees (energies relative to 1, kcal/mol) and first order stationary points [transition wavenumber, cm-1] for insertion of Pd(PH3)2 into substituted haloalkynes.
R-CC-Hal |
RHF/3-21G* |
RHF/DZVP |
RB3LYP/DZVP |
||||
R |
Hal |
Stationary point |
E (DE ) |
Stationary point |
E (DE ) |
Stationary point |
E (DE ) |
H |
F |
1 |
1 |
-5797.7672 (0)/-6032.0060a |
1 |
-5802.5714 (0) {6038.5230}a |
|
|
|
2 |
2 |
-5797.6765 (56.9)/[541.0] {-6031.9293 (48.2)}a |
2 |
-5802.5271 (27.8) {-6038.4894 (21.1)}a |
|
|
|
3 |
3 |
3 |
|||
H |
Cl |
1 |
1 |
1 |
|||
|
|
2 |
2 |
2 |
|||
|
|
3 |
3 |
3 |
|||
H |
Br |
1 |
1 |
1 |
|||
|
|
2 |
2 |
2 |
|||
|
|
3 |
3 |
3 |
|||
H |
I |
1 |
1 |
1 |
|||
|
|
2 |
- |
2 |
2 |
||
|
|
3 |
3 |
3 |
|||
NO2 |
F |
1 |
1 |
1 |
-6007.0821 (0) [-6007.0796]b |
||
|
|
4 |
- |
4 |
4 |
- |
|
|
|
5 |
5 |
5 |
|||
|
|
6 |
- |
6 |
- |
6 |
[-6007.0772]b |
|
|
7 |
- |
7 |
7 |
||
|
|
8 |
- |
8 |
- |
8 |
[-6007.0895]b |
|
|
2 |
2 |
2 |
-6007.0660 (10.10) [328.3] |
||
|
|
3 |
3 |
3 |
-6007.1082 (-16.4) [-6007.1277 (-30.2)]b |
||
CN |
F |
1 |
1 |
1 |
|||
|
|
5 |
5 |
5 |
|||
|
|
2 |
2 |
2 |
|||
|
|
3 |
3 |
3 |
|||
NH2 |
F |
1 |
1 |
1 |
|||
|
|
2 |
2 |
2 |
Table 2: Total Energies, Hartrees (energies relative to 1, kcal/mol) and transition states 2 [transition wavenumber, cm-1] for insertion of Pd(PH3)2 into aryl fluorides
R-aryl-F |
RB3LYP/DZVP |
|||
R |
|
E/Hartree, gas phase. |
E/Hartree, COSMO |
|
H |
1 |
-5957.5331 |
||
|
2 |
-5957.4691 (40.2) |
||
Cr(CO)3 |
1 |
-7341.9592 |
||
|
7 |
a |
optimises to 1 or 3a |
|
|
2 |
-7341.8909 (40.0) [322.4] |
-7341.8987 (37.8) |
|
|
3 |
-7341.9335 (13.4) |
[-7341.9516 (4.7)]a |
|
2-NO2 |
1 |
-6162.0629 |
||
|
7 |
a |
- [-6162.0267 (22.7)]a |
|
|
2 |
-6162.0159 (29.4) |
||
4-NO2 |
1 |
-6162.0738 |
||
|
2 |
-6162.0178 (35.1) |
||
2,4-NO2 |
1 |
-6366.5892 |
||
|
7 |
a |
- [-6366.5747 (9.1)]a |
|
|
2 |
-6366.5605 (18.0) |
||
|
3 |
[-6366.5957 (-4.1)]a |
||
2-CN |
1 |
-6049.7801 |
||
|
7 |
a |
optimises to 1 or 3a |
|
|
2 |
-6049.7219 (36.5) |
||
4-CN |
1 |
-6049.7861 |
||
|
2 |
-6049.7258 (37.8) |