Supplementary Material (ESI) for Perkin Transactions 2. This journal is the Royal Society of Chemistry 2002A Computational Study of the Mechanism of Palladium Insertion into Alkynyl and Aryl Carbon-Fluorine bonds

A Computational Study of the Mechanism of Palladium Insertion into Alkynyl and Aryl Carbon-Fluorine bonds

Markus Jakt, Linus Johannissen, Henry S. Rzepa*, David A. Widdowson and René Wilhelm

Department of Chemistry, Imperial College of Science, Technology and Medicine, London, SW7 2AY.

Supplemental Data

Coordinates are available in PDB or XYZ format, and can be separately viewed using any program capable of reading these formats or within the browser windows using e.g. Chime (http://www.mdlchime.com/ )
Various stationary points on potential surface
Scheme 2

Structures for  points on potential surface
Scheme 3

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

-5771.4516 (0)

1

-5797.7672 (0)/-6032.0060a

1

-5802.5714 (0) {6038.5230}a

 

 

2

-5771.3991 (32.9) [486.4]

2

-5797.6765 (56.9)/[541.0] {-6031.9293 (48.2)}a

2

-5802.5271 (27.8) {-6038.4894 (21.1)}a

 

 

3

-5771.4790 (-17.2)

3

-5797.7611 (-3.8)

3

-5802.5834 (-7.5)

H

Cl

1

-6129.9664 (0)

1

-6157.7692 (0)

1

-6162.8895 (0)

 

 

2

-6129.9337 (20.5) [382.5]

2

-6157.7099 (37.21) [465.3]

2

-6162.8671 (14.07) [195.8]

 

 

3

-6130.0123 (-28.8)

3

-6157.7835 (-9.0)

3

-6162.9161 (-16.7)

H

Br

1

-8232.8362 (0)

1

-8270.2062 (0)

1

-8276.4155 (0)

 

 

2

-8232.8255 (6.7) [260.2]

2

-8270.1619 (27.80) [346.3]

2

-8276.4038 (7.33) [109.4]

 

 

3

-8232.8923 (-35.2)

3

-8270.2303 (-15.1)

3

-8276.4502 (-21.8)

H

I

1

-12560.4793 (0)

1

-12615.4775 (0)

1

-12622.5911 (0)

 

 

2

-

2

-12615.4473 (19.0) [265.5]

2

-12622.5867 (2.75) [62.7]

 

 

3

-12560.5280 (-30.6)

3

-12615.5030 (-16.0)

3

-12622.6270 (-22.5)

NO2

F

1

-5973.7081 (0)

1

-6001.2184 (0)

1

-6007.0821 (0) [-6007.0796]b

 

 

4

-

4

-6001.2124 (3.77) [153.4]

4

-

 

 

5

-5973.7470 (-24.4)

5

-6001.2318 (-8.4)

5

-6007.1271 (-28.2)

 

 

6

-

6

-

6

[-6007.0772]b

 

 

7

-

7

-6001.1880 (19.1)

7

-6007.0759 (3.9) [-6007.0967 (-10.8)]b

 

 

8

-

8

-

8

[-6007.0895]b

 

 

2

-5973.6910 (10.7) [375.2]

2

-6001.1645 (33.82) [478.8]

2

-6007.0660 (10.10) [328.3]

 

 

3

-5973.7551 (-29.5)

3

-6001.2284 (-6.3)

3

-6007.1082 (-16.4) [-6007.1277 (-30.2)]b

CN

F

1

-5862.6693 (0)

1

-5889.4958 (0)

1

-5894.8206 (0)

 

 

5

-5862.6910 (-13.6)

5

-5889.4980 (-1.38)

5

-5894.8543 (-21.2)

 

 

2

-5862.6374 (20.02) [405.3]

2

-5889.4276 (42.80) [498.8]

2

-5894.7956 (15.69) [376.3]

 

 

3

-5862.7091 (-25.0)

3

-5889.5028 (-4.4)

3

-5894.8442 (-14.8)

NH2

F

1

-5826.1742 (0)

1

-5852.7885 (0)

1

-5857.9280

 

 

2

-5826.1241 (31.4) [442.6]

2

-5852.7048 (52.5) (488.12cm-1)

2

-5857.8866 (26.0) [286.2]

a Results for R'=Me (PMe3). b COSMO Solvation model with geometry optimisation, using LOOSE convergence criteria.

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

-5957.5279 (0)

-5957.5331

 

2

-5957.4622 (41.2) [360.7]

-5957.4691 (40.2)

Cr(CO)3

1

-7341.9547 (0)

-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

-6162.0548 (0)

-6162.0629

 

7

a

- [-6162.0267 (22.7)]a

 

2

-6162.0101 (28.1) [296.4]

-6162.0159 (29.4)

4-NO2

1

-6162.0661 (0)

-6162.0738

 

2

-6162.0096 (35.5) [336.2]

-6162.0178 (35.1)

2,4-NO2

1

-6366.5868 (0)

-6366.5892

 

7

a

- [-6366.5747 (9.1)]a

 

2

-6366.5520 (21.8) [278.0]a

-6366.5605 (18.0)

 

3

[-6366.5785 (5.2)]a

[-6366.5957 (-4.1)]a

2-CN

1

-6049.7744 (0)

-6049.7801

 

7

a

optimises to 1 or 3a

 

2

-6049.7180 (35.5) [341.5]

-6049.7219 (36.5)

4-CN

1

-6049.7778 (0)

-6049.7861

 

2

-6049.7188 (37.02) [343.9]

-6049.7258 (37.8)

a Geometry optimised (to LOOSE tolerances) with COSMO model. Geometry not locatable with gas phase model