Directory UMM :wiley:Public:journals:jcc:suppmat:18:

Supplementary Materials

(1) Detailed geometries of all structures and energies studied.

(2) Table 4 : MP2 calculated positional charge densities (q in electronic unit) and dipole moment ( in Debye) for the direct tautomerization processes by NBO method.

Table 5 : MP2 calculated energy value of non-catalyzed hydrogen

transfer reaction by the SCRF method.

Table 6 : Energies for the water catalyzed enolization reactions.

Table 7 : MP2 (MP2/6-31G

**

_//MP2/6-31G

**

_{) calculated energy values for}

Table 4. MP2 calculated positional charge densities (q in electronic

R keto TS enol keto TS enol

C1 _{0.681 0.671 0.416}

*(a) E. D. Glendenning, A. E. Reed, E. Carpenter and F. Weinhold, NBO version 3.1 in

Gaussian 92. (b) A. E. Reed, L. A. Curtiss and F. Weinhold, Chem. Rev., 88, 899

Table 5. MP2 calculated energy values of non-catalyzed hydrogen

transfer

reaction by SCRF method.(a)

keto (hartree) TS (hartree) enol (hartree) _E _{(kcal/mol) E}o _(kcal/mol)

Table 6. Energetics for the water catalyzed enolization reactions.

keto (hartree) TS (hartree) enol (hartree) _E _{(kcal/mol) E}o _(kcal/mol)

(a) _{-268.00564 -267.90696 -267.98132 61.92 15.26}

CH3 (b) -268.80449 -268.73251 -268.77983 45.17 15.47

(c) _{-268.93974 -268.87018 -268.91949 43.08 12.71}

(a) _{-228.95564 -228.85807 -228.93528 61.22 12.78}

H (b) _{-229.61084 -229.53954 -229.58918 44.75 13.60}

(c) _{-229.73928 -229.66381 -229.71709 43.37 9.94}

(a) _{-327.83576 -327.73454 -327.79096 63.51 28.11}

F (b) _{-328.65312 -328.57410 -328.60882 49.58 27.79}

(c) _{-328.84222 -328.76492 -328.80362 48.51 24.22}

(a) _{-320.67867 -320.58672 -320.66563 57.71 8.19}

CN (b) _{-321.60699 -321.53990 -321.59202 42.10 9.39}

(c) _{-321.76211 -321.69697 -321.75200 40.88 6.34}

(a) HF/6-31G**_//HF/6-31G**

(b) MP2/6-31G**_//MP2/6-31G**

Table 7. MP2 (MP2/6-31G

**

_//MP2/6-31G

**

_{) calculated energy values for}

-268.80742 -268.73343 -268.78205 46.43 15.92 (8.33)(b)

-229.61317 -229.54063 -229.59221 45.52 13.15

H 10.87

-229.61332 -229.54070 -229.59240 45.57 13.13 (6.23)

-328.65411 -328.57609 -328.61548 48.96 24.24

F 20.02

-328.65417 -328.57622 -328.61590 48.92 24.02

-321.60803 -321.54463 -321.60349 39.79 2.85

CN 2.74

-321.60810 -321.54495 -321.60424 39.63 2.42

(a) Upper values are for  = 20.7 and lower values for  = 78.5