PDF《water†》

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2006 Catalytic homogeneous hydrogenation of compounds containing Х→О semipolar bonds (X = N, S, P) with para- hydrogen as a promising route for preparation of para- water? Yuri A.

Ustynyuk,*Аlexei V. Gavrikov, and Nikolay М. Sergeyev Electronic Supplementary Information (ESI) Calculations details. Stationary points were identified by an analysis of Hessians. The energies of the stationary points are corrected to zero-point vibrations (ZPVE). The statistical formulas of rigid rotator and harmonic oscillator were used for the calculation of the thermodynamic functions. Construction of internal reaction coordinate (IRC) was used to check the observed transition states. Table 1. Calculated thermodynamic functions of the reactants, intermediates, and reaction products (all Hessian eigenvalues are positive, and the stationary points are minima on the PES) E, a.u** E0, a.u S0 298, cal*mol-1 *K-1 U0 298-E, kcal*mol-1 H0 298-E, kcal*mol-1 G0 298-E, kcal*mol-1 ClRh(PPh3)3 -478.116 -477.312 323.5 539.1 539.7 443.3 ClRh(PPh3)2(1) -360.433 -359.899 243.7 359.5 360.1 287.4 ClRh(PPh3)2 (1T)* -360.408 -359.873 255.0 360.0 360.6 284.6 ClRh(PPh3)2H2(2) -361.645 -361.094 255.1 370.5 371.0 295.0 ClRh(PPh3)2H2 (2T) -361.586 -361.038 252.0 369.0 369.6 294.4 ClRh(PPh3)2(OH)H(4) -377.661 -377.104 256.1 375.0 375.6 299.2 ClRh(PPh3)2(OH)H (4T) -377.624 -377.068 257.1 374.2 374.8 298.2 ClRh(PPh3)2(OH2)(6) -377.667 -377.106 252.1 377.4 377.9 302.8 H2 -1.166 -1.157 32.6 7.6 8.2 -1.5 H2O -17.213 -17.192 46.5 14.9 15.5 1.6 C5H5NO -57.255 -57.165 73.8 59.9 60.5 38.5 C5H5N -41.285 -41.199 69.2 56.8 57.4 36.8 C5H5N*H2O -58.511 -58.401 89.3 74.0 74.6 48.0 Ph3PO -133.693 -133.423 140.8 180.5 181.1 139.1 Ph3P -117.644 -117.378 135.5 177.0 177.6 137.2 (CH3)2SO -41.077 -41.000 74.9 51.7 52.2 29.9 (CH3)2S -25.090 -25.017 69.4 49.2 49.8 29.1 N2O -35.835 -35.825 52.6 8.5 9.0 -6.6 N2 -19.888 -19.883 47.2 4.8 5.4 -8.6 *The index (T) is used to designate the triplet state. **a.u. = 627.52 kcal/mol