suppmat_tables. 14KB Jun 05 2011 09:30:47 PM
SUPPLEMENTARY MATERIAL
Computational Study on the Nature of the
Transition Structure for Oxygen Transfer from
Dioxirane and Carbonyl Oxide
___________________________________________________________________
Anwar G. Baboul, H. Bernhard Schlegel,
Mikhail N. Glukhovtsev and Robert D. Bach
2
TABLE IS.___________________________________________________
Total Energies of Nucleophiles and Oxidants: Dioxirane (DO), Dimethyl Dioxirane
(DMDO), Carbonyl Oxide (CO) and Dimethyl Carbonyl Oxide (DMCO) Calculated
at Various Levels of Theory as well as Their Dipole Moments.a
____________________________________________________________________
MP2
MP4
QCISD(T)
B3LYP
____________________________________________________________________
DO
-189.09807 -189.12969 -189.12811 -189.61555
3.2
DMDO
-267.45662 -267.51981 -267.51813 -268.26894
3.9
CO
-189.04309 -189.08318 -189.08264
5.1
DMCO
-267.40429 -267.47539 -267.47635
7.1
formaldehyde
acetone
oxirane
-114.16775
-192.52035
-153.30358
-114.19202
-192.57647
-153.34147
-114.19111
-192.57542
-153.34140
-114.50047
-193.15242
2.9
3.6
2.7
H2S
Me2S
H2SO
H2SO2
Me2SO
Me2SO2
-398.78841
-477.12111
-473.74744
-548.77731
-552.11218
-627.15421
-398.81200
-477.17503
-473.76730
-548.80744
-552.17242
-398.81340
-399.38544
-478.01381
-474.52844
-549.73047
-553.18693
-628.40082
1.8
NH3
NH3O
Me3N
Me3NO
-56.35421
-131.27737
-173.82860
-248.78953
-56.37127
-131.30269
-173.89367
-56.37211
-131.30374
PH3
PH3O
Me3P
Me3PO
-342.55171
-417.59563
-460.06870
-535.15044
-342.57831
-417.62272
-460.14063
-342.58062
-417.62211
-78.28503
-78.31983
-78.32215
H2C=CH2
-473.77665
-548.80404
4.7
4.3
2.2
6.7
-174.47441
-249.61560
1.3
4.8
-461.09840
-536.35300
-78.58746
_______________________________________________________________________
3
a
Total energies are in hartrees calculated with the 6-31G* basis set; MP2, MP4 and
QCISD(T) energies at the MP2 optimized geometry and the B3LYP energies at the
B3LYP optimized geometries, dipole moments calculated at the HF/6-31G* level of
theory are in Debyes.
4
TABLE IIS.__________________________________________________
Total Energies for Transition Structures for Reactions of Nucleophiles with
Oxidants: Dioxirane (DO), Dimethyl Dioxirane (DMDO), Carbonyl Oxide (CO) and
Dimethyl Carbonyl Oxide (DMCO) Calculated at Various Levels of Theory as well
as the Dipole Moments of the Transition Structures.a
____________________________________________________________________
MP2
MP4
QCISD(T)
B3LYP
____________________________________________________________________
H2S + DO
-587.84301 -587.90321 -587.90184 -588.97014
11.6
H2S + DMDO
-666.19707 -666.28923 -666.28773 -667.61589
14.3
Me2S + DMDO
-744.55791 -747.67989
-746.26690
8.7
H2S + CO
-587.80223 -587.86889 -587.87244
3.2
H2S + DMCO
-666.16485 -666.26351 -666.26648
5.2
H2SO + DO
H2SO + DMDO
Me2SO + DMD
H2SO + CO
H2SO + DMCO
-662.82596
-741.18086
-819.55392
-662.77835
-741.14031
-662.89047
-741.27736
-819.68242
-662.84965
-741.24355
NH3 + DO
NH3 + DMDO
Me3N + DMDO
NH3 + CO
NH3+DMCO
-245.40971
-323.76519
-441.26818
-245.36742
-323.72870
-245.46541
-323.85303
-441.40345
-245.42808
-323.82164
PH3 + DO
PH3 + DMDO
Me3P + DMDO
PH3 + CO
PH3 + DMCO
-531.63841
-609.99423
-727.52449
-531.57620
-609.94233
-531.69546
-610.08289
-727.65890
-531.64374
-610.04135
H2C=CH2 + DO
-267.36172
H2C=CH2 + DMDO -345.72437
-267.42798
-345.83518
-662.88093
-741.26788
-664.12688
-742.77475
-821.44059
-662.85094
-741.24386
-245.46479
-323.85227
11.0
-246.13831
-324.78549
-442.72623
12.6
12.8
8.6
3.0
4.4
-532.74402
5.8
12.0
3.2
4.8
6.8
-245.43206
-323.82482
-531.69354
-610.08030
-611.39084
-729.36224
-531.64861
-610.04483
7.2
5.9
6.0
5.4
11.1
5
H2C=CH2 + CO
-267.30460
H2C=CH2+DMCO -345.66874
-267.38092
5.1
6.2
_____________________________________________________________
a
Total energies are in hartrees calculated with the 6-31G* basis set; MP2, MP4 and
QCISD(T) energies at the MP2 optimized geometry and the B3LYP energies at the
B3LYP optimized geometries, dipole moments calculated at the HF/6-31G* level of
theory are in Debyes.
6
TABLE IIIS._________________________________________________
The Lowest Eigenvalues of Stability Matrix Calculated for the RHF Solutions of
The Transition Structures for Oxidation of Nucleophiles by Dioxirane (DO),
Dimethyl Dioxirane (DMDO), Carbonyl and Dimethyl Carbonyl Oxides (DMCO).
___________________________________________________________________
Stability
Roots for stable
S2
ŒEa
root
wavefunctions
____________________________________________________________________
H2S + DO
-0.0405407
0.0322942
0.816
-12.2
H2S + DMDO
-0.0332855
0.0372173
0.781
-9.31
Me2S + DMDO
-0.0425741
H2SO + DO
H2SO + DMDO
Me2SO + DMDO
-0.1245621
-0.1122951
-0.0805993
0.0270703
0.0304930
0.946
0.921
-37.61
-31.85
NH3 + DO
NH3 + DMDO
Me3N + DMDO
-0.0008955
0.0063566
-0.0380976
0.0332519
0.0063426
0.0298789
0.619
0
-1.20
0.00
PH3 + DO
PH3 + DMDO
Me3P + DMDO
-0.1742695
-0.1724804
-0.1495927
0.0406655
0.0400925
0.805
0.825
-30.54
-31.54
H2S + carbonyl oxide
H2S + DMCO
-0.0079827
-0.0004476
0.0010353
0.0009064
0.109
0.006
-0.14
0.00
H2SO + carbonyl oxide 0.0058506
H2SO + DMCO
0.0251668
0.0058506
0.0251620
0
0
NH3 + DMDO
NH3 + DO
0.0007418
0.0022123
0.075
0.147
-0.0056689
-0.0088571
0.00
0.00
-0.07
-0.18
PH3 + carbonyl oxide 0.0005017
0.0005016
0
0.00
PH3 + DMCO
0.0304917
0.0304832
0
0.00
_______________________________________________________________________
7
a in kcal/mol obtained by calculating the difference in energies using the unstable and
stable wavefunctions at the HF/6-31G* level of theory.
Computational Study on the Nature of the
Transition Structure for Oxygen Transfer from
Dioxirane and Carbonyl Oxide
___________________________________________________________________
Anwar G. Baboul, H. Bernhard Schlegel,
Mikhail N. Glukhovtsev and Robert D. Bach
2
TABLE IS.___________________________________________________
Total Energies of Nucleophiles and Oxidants: Dioxirane (DO), Dimethyl Dioxirane
(DMDO), Carbonyl Oxide (CO) and Dimethyl Carbonyl Oxide (DMCO) Calculated
at Various Levels of Theory as well as Their Dipole Moments.a
____________________________________________________________________
MP2
MP4
QCISD(T)
B3LYP
____________________________________________________________________
DO
-189.09807 -189.12969 -189.12811 -189.61555
3.2
DMDO
-267.45662 -267.51981 -267.51813 -268.26894
3.9
CO
-189.04309 -189.08318 -189.08264
5.1
DMCO
-267.40429 -267.47539 -267.47635
7.1
formaldehyde
acetone
oxirane
-114.16775
-192.52035
-153.30358
-114.19202
-192.57647
-153.34147
-114.19111
-192.57542
-153.34140
-114.50047
-193.15242
2.9
3.6
2.7
H2S
Me2S
H2SO
H2SO2
Me2SO
Me2SO2
-398.78841
-477.12111
-473.74744
-548.77731
-552.11218
-627.15421
-398.81200
-477.17503
-473.76730
-548.80744
-552.17242
-398.81340
-399.38544
-478.01381
-474.52844
-549.73047
-553.18693
-628.40082
1.8
NH3
NH3O
Me3N
Me3NO
-56.35421
-131.27737
-173.82860
-248.78953
-56.37127
-131.30269
-173.89367
-56.37211
-131.30374
PH3
PH3O
Me3P
Me3PO
-342.55171
-417.59563
-460.06870
-535.15044
-342.57831
-417.62272
-460.14063
-342.58062
-417.62211
-78.28503
-78.31983
-78.32215
H2C=CH2
-473.77665
-548.80404
4.7
4.3
2.2
6.7
-174.47441
-249.61560
1.3
4.8
-461.09840
-536.35300
-78.58746
_______________________________________________________________________
3
a
Total energies are in hartrees calculated with the 6-31G* basis set; MP2, MP4 and
QCISD(T) energies at the MP2 optimized geometry and the B3LYP energies at the
B3LYP optimized geometries, dipole moments calculated at the HF/6-31G* level of
theory are in Debyes.
4
TABLE IIS.__________________________________________________
Total Energies for Transition Structures for Reactions of Nucleophiles with
Oxidants: Dioxirane (DO), Dimethyl Dioxirane (DMDO), Carbonyl Oxide (CO) and
Dimethyl Carbonyl Oxide (DMCO) Calculated at Various Levels of Theory as well
as the Dipole Moments of the Transition Structures.a
____________________________________________________________________
MP2
MP4
QCISD(T)
B3LYP
____________________________________________________________________
H2S + DO
-587.84301 -587.90321 -587.90184 -588.97014
11.6
H2S + DMDO
-666.19707 -666.28923 -666.28773 -667.61589
14.3
Me2S + DMDO
-744.55791 -747.67989
-746.26690
8.7
H2S + CO
-587.80223 -587.86889 -587.87244
3.2
H2S + DMCO
-666.16485 -666.26351 -666.26648
5.2
H2SO + DO
H2SO + DMDO
Me2SO + DMD
H2SO + CO
H2SO + DMCO
-662.82596
-741.18086
-819.55392
-662.77835
-741.14031
-662.89047
-741.27736
-819.68242
-662.84965
-741.24355
NH3 + DO
NH3 + DMDO
Me3N + DMDO
NH3 + CO
NH3+DMCO
-245.40971
-323.76519
-441.26818
-245.36742
-323.72870
-245.46541
-323.85303
-441.40345
-245.42808
-323.82164
PH3 + DO
PH3 + DMDO
Me3P + DMDO
PH3 + CO
PH3 + DMCO
-531.63841
-609.99423
-727.52449
-531.57620
-609.94233
-531.69546
-610.08289
-727.65890
-531.64374
-610.04135
H2C=CH2 + DO
-267.36172
H2C=CH2 + DMDO -345.72437
-267.42798
-345.83518
-662.88093
-741.26788
-664.12688
-742.77475
-821.44059
-662.85094
-741.24386
-245.46479
-323.85227
11.0
-246.13831
-324.78549
-442.72623
12.6
12.8
8.6
3.0
4.4
-532.74402
5.8
12.0
3.2
4.8
6.8
-245.43206
-323.82482
-531.69354
-610.08030
-611.39084
-729.36224
-531.64861
-610.04483
7.2
5.9
6.0
5.4
11.1
5
H2C=CH2 + CO
-267.30460
H2C=CH2+DMCO -345.66874
-267.38092
5.1
6.2
_____________________________________________________________
a
Total energies are in hartrees calculated with the 6-31G* basis set; MP2, MP4 and
QCISD(T) energies at the MP2 optimized geometry and the B3LYP energies at the
B3LYP optimized geometries, dipole moments calculated at the HF/6-31G* level of
theory are in Debyes.
6
TABLE IIIS._________________________________________________
The Lowest Eigenvalues of Stability Matrix Calculated for the RHF Solutions of
The Transition Structures for Oxidation of Nucleophiles by Dioxirane (DO),
Dimethyl Dioxirane (DMDO), Carbonyl and Dimethyl Carbonyl Oxides (DMCO).
___________________________________________________________________
Stability
Roots for stable
S2
ŒEa
root
wavefunctions
____________________________________________________________________
H2S + DO
-0.0405407
0.0322942
0.816
-12.2
H2S + DMDO
-0.0332855
0.0372173
0.781
-9.31
Me2S + DMDO
-0.0425741
H2SO + DO
H2SO + DMDO
Me2SO + DMDO
-0.1245621
-0.1122951
-0.0805993
0.0270703
0.0304930
0.946
0.921
-37.61
-31.85
NH3 + DO
NH3 + DMDO
Me3N + DMDO
-0.0008955
0.0063566
-0.0380976
0.0332519
0.0063426
0.0298789
0.619
0
-1.20
0.00
PH3 + DO
PH3 + DMDO
Me3P + DMDO
-0.1742695
-0.1724804
-0.1495927
0.0406655
0.0400925
0.805
0.825
-30.54
-31.54
H2S + carbonyl oxide
H2S + DMCO
-0.0079827
-0.0004476
0.0010353
0.0009064
0.109
0.006
-0.14
0.00
H2SO + carbonyl oxide 0.0058506
H2SO + DMCO
0.0251668
0.0058506
0.0251620
0
0
NH3 + DMDO
NH3 + DO
0.0007418
0.0022123
0.075
0.147
-0.0056689
-0.0088571
0.00
0.00
-0.07
-0.18
PH3 + carbonyl oxide 0.0005017
0.0005016
0
0.00
PH3 + DMCO
0.0304917
0.0304832
0
0.00
_______________________________________________________________________
7
a in kcal/mol obtained by calculating the difference in energies using the unstable and
stable wavefunctions at the HF/6-31G* level of theory.