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(1)

Computational Study on the Nature of the

Transition Structure for Oxygen Transfer from

Dioxirane and Carbonyl Oxide

___________________________________________________________________

(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 <µ> ____________________________________________________________________ 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 -114.16775 -114.19202 -114.19111 -114.50047 2.9 acetone -192.52035 -192.57647 -192.57542 -193.15242 3.6 oxirane -153.30358 -153.34147 -153.34140 2.7

H2S -398.78841 -398.81200 -398.81340 -399.38544 1.8 Me2S -477.12111 -477.17503 -478.01381

H2SO -473.74744 -473.76730 -473.77665 -474.52844 4.7 H2SO2 -548.77731 -548.80744 -548.80404 -549.73047 4.3 Me2SO -552.11218 -552.17242 -553.18693

Me2SO2 -627.15421 -628.40082

NH3 -56.35421 -56.37127 -56.37211 2.2 NH3O -131.27737 -131.30269 -131.30374 6.7 Me3N -173.82860 -173.89367 -174.47441

Me3NO -248.78953 -249.61560

PH3 -342.55171 -342.57831 -342.58062 1.3 PH3O -417.59563 -417.62272 -417.62211 4.8 Me3P -460.06870 -460.14063 -461.09840

Me3PO -535.15044 -536.35300

H2C=CH2 -78.28503 -78.31983 -78.32215 -78.58746

(3)

a Total energies are in hartrees calculated with the 6-31G* basis set; MP2, MP4 and

(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 <µ> ____________________________________________________________________ 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 -662.82596 -662.89047 -662.88093 -664.12688 7.2 H2SO + DMDO -741.18086 -741.27736 -741.26788 -742.77475 5.9 Me2SO + DMD -819.55392 -819.68242 -821.44059 6.0 H2SO + CO -662.77835 -662.84965 -662.85094

H2SO + DMCO -741.14031 -741.24355 -741.24386 11.0

NH3 + DO -245.40971 -245.46541 -245.46479 -246.13831 12.6 NH3 + DMDO -323.76519 -323.85303 -323.85227 -324.78549 12.8 Me3N + DMDO -441.26818 -441.40345 -442.72623 8.6 NH3 + CO -245.36742 -245.42808 -245.43206 3.0 NH3+DMCO -323.72870 -323.82164 -323.82482 4.4

PH3 + DO -531.63841 -531.69546 -531.69354 -532.74402 5.8 PH3 + DMDO -609.99423 -610.08289 -610.08030 -611.39084 12.0 Me3P + DMDO -727.52449 -727.65890 -729.36224 3.2 PH3 + CO -531.57620 -531.64374 -531.64861 4.8 PH3 + DMCO -609.94233 -610.04135 -610.04483 6.8

(5)

H2C=CH2 + CO -267.30460 -267.38092 5.1 H2C=CH2+DMCO -345.66874 6.2

_____________________________________________________________

a Total energies are in hartrees calculated with the 6-31G* basis set; MP2, MP4 and

(6)

TABLE IIIS._________________________________________________

The Lowest Eigenvalues of Stability Matrix Calculated for the RHF Solutionsof 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 -0.1245621 0.0270703 0.946 -37.61 H2SO + DMDO -0.1122951 0.0304930 0.921 -31.85 Me2SO + DMDO -0.0805993

NH3 + DO -0.0008955 0.0332519 0.619 -1.20 NH3 + DMDO 0.0063566 0.0063426 0 0.00 Me3N + DMDO -0.0380976 0.0298789

PH3 + DO -0.1742695 0.0406655 0.805 -30.54 PH3 + DMDO -0.1724804 0.0400925 0.825 -31.54 Me3P + DMDO -0.1495927

H2S + carbonyl oxide -0.0079827 0.0010353 0.109 -0.14 H2S + DMCO -0.0004476 0.0009064 0.006 0.00

H2SO + carbonyl oxide 0.0058506 0.0058506 0 0.00 H2SO + DMCO 0.0251668 0.0251620 0 0.00

NH3 + DMDO -0.0056689 0.0007418 0.075 -0.07 NH3 + DO -0.0088571 0.0022123 0.147 -0.18

(7)

a in kcal/mol obtained by calculating the difference in energies using the unstable and

Gambar

TABLE IS.___________________________________________________
TABLE IIS.__________________________________________________

Referensi

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