"Regioselective Oxidative Ring Opening of Cyclopropyl Silyl Ethers" by H. Rinderhagen, J. Mattay,* R. Nussbaum and T. Bally* SUPPORTING INFORMATION ********************** Complete Reference 21 (Gaussian Program): M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A. Pople, Gaussian 03, Rev E.01, Gaussian, Inc., Wallingford CT, 2004. Energies and geometries of all stationary points located and characterized in the course of the above study Note: All structures are optimized in vacuum, with energies in hartree, unless otherwise noted. If no "low frequencies" are given, the stationary points are potential energy minima. The trimethyl silyl group makes it practically im- possible to "quench" geometries to their usual thresholds, but the maximum and rms forces were in all cases below the thresholds. ------------------------------------------------------ Neutral 1-trimethylsilyloxybicyclo[4.1.0]- heptane (A) Method: B3LYP Basis set: 6-31G(d) HF=-757.875679 6 -1.683097 -1.289358 -0.302494 6 -3.169968 -0.956772 -0.451654 6 -3.448029 0.552410 -0.564505 6 -2.636410 1.357262 0.458057 6 -1.129340 1.220962 0.185541 1 -3.568176 -1.466143 -1.337259 1 -1.301613 -2.059569 -0.968367 1 -3.182089 0.899448 -1.573060 1 -4.521494 0.742123 -0.439492 1 -2.913125 2.417915 0.418001 1 -2.875710 1.015985 1.475528 1 -0.894161 1.736868 -0.755232 1 -0.552028 1.722567 0.974986 1 -3.723450 -1.363582 0.406597 6 -0.667286 -0.221112 0.031830 6 -1.018964 -1.258545 1.066817 1 -0.275594 -2.019271 1.285154 1 -1.626340 -0.964491 1.921383 8 0.572022 -0.365106 -0.621768 14 2.110050 0.048501 -0.086652 6 2.392033 -0.478359 1.706525 1 3.399640 -0.191736 2.033579 1 1.677377 -0.007166 2.391168 1 2.301079 -1.563993 1.827833 6 3.267036 -0.884476 -1.241597 1 3.086264 -0.607082 -2.286477 1 4.317990 -0.666559 -1.014885 1 3.122643 -1.967590 -1.156569 6 2.417601 1.906714 -0.248448 1 2.215300 2.253086 -1.268813 1 1.790741 2.493906 0.432234 1 3.464414 2.144766 -0.019464 Low frequencies --- -23.2499 -0.0009 -0.0007 0.0017 3.1397 11.3660 Sum of electronic and zero-point Energies= -757.592962 Sum of electronic and thermal Energies= -757.577937 Sum of electronic and thermal Enthalpies= -757.576992 Sum of electronic and thermal Free Energies= -757.635530 -------------------------------------------------------- Transition State (B) Method: B3LYP Basis set: 6-31G(d) HF=-757.602072 6 0.659564 0.320899 0.183819 6 1.753666 1.332170 -0.299044 6 3.117156 0.747589 -0.713652 6 3.185553 -0.788566 -0.704955 6 2.535123 -1.372269 0.554360 6 1.022500 -1.091613 0.558473 6 1.451629 1.595433 1.099031 8 -0.571041 0.674696 -0.086841 14 -2.189012 -0.093844 -0.106819 6 -2.184856 -1.237704 -1.590364 6 -2.431241 -0.967155 1.533394 6 -3.284769 1.399542 -0.319431 1 3.344351 1.126493 -1.714981 1 1.293411 2.031902 -0.995038 1 2.681724 -1.192277 -1.593145 1 4.233362 -1.096298 -0.772778 1 2.684105 -2.455073 0.603978 1 3.008359 -0.958428 1.454603 1 0.532952 -1.739858 -0.182263 1 0.571038 -1.340300 1.528597 1 3.878389 1.155491 -0.039262 1 0.722374 2.347778 1.379446 1 2.062645 1.169346 1.890038 1 -3.483222 -1.271232 1.609941 1 -1.827675 -1.874199 1.638783 1 -2.227136 -0.309036 2.385394 1 -3.044060 1.949242 -1.235737 1 -4.334933 1.090483 -0.386225 1 -3.199314 2.090731 0.526129 1 -1.903520 -0.708882 -2.507397 1 -1.523837 -2.102748 -1.471884 1 -3.200471 -1.626850 -1.737794 Low frequencies --- -247.8221 -3.7916 -0.0015 0.0022 0.0024 1.1666 6.6982 Sum of electronic and zero-point Energies= -757.321616 Sum of electronic and thermal Energies= -757.306317 Sum of electronic and thermal Enthalpies= -757.305373 Sum of electronic and thermal Free Energies= -757.364640 PCM-SCFR calculations in acetonitrile: (a.u.) = -757.601311 (a.u.) = -757.667691 Total free energy in solution: with all non electrostatic terms (a.u.) = -757.644401 -------------------------------------------------------------------- (Polarized solute)-Solvent (kcal/mol) = -41.65 -------------------------------------------------------------------- Cavitation energy (kcal/mol) = 26.15 Dispersion energy (kcal/mol) = -12.04 Repulsion energy (kcal/mol) = 0.51 Total non electrostatic (kcal/mol) = 14.61 ------------------------------------------------------------------- Structure (C) Method: B3LYP Basis set: 6-31G(d) HF=-757.615653 6 0.516738 -0.271532 -0.720365 6 2.067925 -1.495652 0.229729 6 3.293291 -0.759770 0.642811 6 3.075896 0.772269 0.810767 6 2.438780 1.449264 -0.411216 6 0.932493 1.165192 -0.582680 6 1.473993 -1.337644 -1.138710 8 -0.676939 -0.655981 -0.458595 14 -2.212546 0.049431 0.174393 6 -1.866819 0.531033 1.950826 6 -2.649892 1.478039 -0.952007 6 -3.352890 -1.414107 0.005629 1 3.675348 -1.172219 1.581462 1 1.515365 -2.104146 0.940610 1 2.462615 0.959053 1.701524 1 4.054551 1.223496 1.003614 1 2.540750 2.534959 -0.312766 1 2.984884 1.179874 -1.323989 1 0.370129 1.613360 0.244988 1 0.568097 1.663844 -1.496578 1 4.069558 -0.907448 -0.123452 1 0.942425 -2.223786 -1.491919 1 2.204328 -0.989444 -1.873846 1 -3.660477 1.826545 -0.703467 1 -1.979654 2.337395 -0.847837 1 -2.666875 1.174752 -2.004895 1 -3.008335 -2.266809 0.600568 1 -4.358622 -1.151826 0.355717 1 -3.441062 -1.738804 -1.036775 1 -1.461047 -0.308129 2.526658 1 -1.185530 1.382482 2.051762 1 -2.812377 0.820116 2.427192 Low frequencies --- -7.2352 -3.2388 -0.0020 -0.0012 -0.0002 2.7569 Sum of electronic and zero-point Energies= -757.334560 Sum of electronic and thermal Energies= -757.318716 Sum of electronic and thermal Enthalpies= -757.317772 Sum of electronic and thermal Free Energies= -757.378144 PCM-SCFR calculations in acetonitrile: (a.u.) = -757.614912 (a.u.) = -757.680294 Total free energy in solution: with all non electrostatic terms (a.u.) = -757.657038 -------------------------------------------------------------------- (Polarized solute)-Solvent (kcal/mol) = -41.03 -------------------------------------------------------------------- Cavitation energy (kcal/mol) = 26.20 Dispersion energy (kcal/mol) = -12.12 Repulsion energy (kcal/mol) = 0.52 Total non electrostatic (kcal/mol) = 14.59 -------------------------------------------------------------------- Structure (D) Method: B3LYP Basis set: 6-31G(d) HF=-757.604615 6 -0.648533 -0.225090 -0.067762 6 -1.720034 -1.236020 -0.368410 6 -3.104699 -0.658006 -0.775187 6 -3.227529 0.867387 -0.604005 6 -2.502632 1.358992 0.654555 6 -0.991422 1.113403 0.515299 6 -1.660480 -1.826233 1.008604 8 0.555391 -0.567770 -0.325380 14 2.223819 0.083104 -0.064258 6 2.442876 0.203439 1.790836 6 3.235628 -1.264104 -0.858525 6 2.310464 1.719742 -0.967447 1 -3.295957 -0.933965 -1.816543 1 -1.324295 -1.950345 -1.096540 1 -2.804339 1.378598 -1.479558 1 -4.285893 1.142117 -0.568909 1 -2.669262 2.429015 0.809716 1 -2.892037 0.853628 1.546954 1 -0.559459 1.849834 -0.179702 1 -0.452539 1.250874 1.462473 1 -3.868279 -1.165449 -0.176184 1 -0.901097 -2.560326 1.256061 1 -2.330007 -1.484472 1.790807 1 4.303689 -1.024668 -0.789472 1 3.081950 -2.230559 -0.366493 1 2.991744 -1.379017 -1.920223 1 1.751043 2.522462 -0.476159 1 3.359673 2.039902 -1.006690 1 1.964642 1.634412 -2.003696 1 1.843731 0.995638 2.251917 1 2.213795 -0.743527 2.291943 1 3.494464 0.433486 2.005220 Low frequencies --- -3.3150 -0.0021 -0.0021 -0.0020 1.8540 7.6716 Sum of electronic and zero-point Energies= -757.324782 Sum of electronic and thermal Energies= -757.308539 Sum of electronic and thermal Enthalpies= -757.307595 Sum of electronic and thermal Free Energies= -757.369190 PCM-SCFR calculations in acetonitrile: (a.u.) = -757.604000 (a.u.) = -757.669538 Total free energy in solution: with all non electrostatic terms (a.u.) = -757.645971 -------------------------------------------------------------------- (Polarized solute)-Solvent (kcal/mol) = -41.13 -------------------------------------------------------------------- Cavitation energy (kcal/mol) = 26.34 Dispersion energy (kcal/mol) = -12.06 Repulsion energy (kcal/mol) = 0.51 Total non electrostatic (kcal/mol) = 14.79 -------------------------------------------------------- Transition State (E) Method: B3LYP Basis set: 6-31G(d) HF=-757.600127 (-757.6000478) 6 0.666538 0.146474 -0.086090 6 1.739767 1.185417 -0.366930 6 3.193138 0.668263 -0.218063 6 3.342649 -0.835482 -0.467145 6 2.447829 -1.608860 0.505987 6 0.967072 -1.278336 0.260425 6 1.458751 2.375699 0.510516 8 -0.530164 0.537837 -0.224918 14 -2.227092 -0.099910 -0.024501 6 -2.357201 -1.617645 -1.109953 6 -2.411550 -0.414921 1.809472 6 -3.198906 1.359574 -0.649940 1 3.827948 1.248667 -0.893901 1 1.550281 1.469863 -1.416341 1 3.084428 -1.088686 -1.505473 1 4.388683 -1.125331 -0.327473 1 2.583240 -2.689738 0.404448 1 2.718234 -1.353331 1.537702 1 0.603584 -1.841390 -0.616572 1 0.317696 -1.590592 1.089051 1 3.541879 0.889089 0.798420 1 0.694708 3.096906 0.246547 1 1.951149 2.457277 1.473415 1 -3.465709 -0.635053 2.021942 1 -1.828984 -1.269127 2.170053 1 -2.141484 0.466219 2.401699 1 -2.963528 1.585476 -1.695619 1 -4.273593 1.147797 -0.592787 1 -3.007882 2.258251 -0.053708 1 -2.014641 -1.423254 -2.132586 1 -1.818711 -2.485933 -0.717175 1 -3.415226 -1.902162 -1.178953 Low frequencies --- -75.8003 -2.8712 -1.1460 -0.0015 0.0020 0.0021 4.1346 Sum of electronic and zero-point Energies= -757.321429 Sum of electronic and thermal Energies= -757.305673 Sum of electronic and thermal Enthalpies= -757.304729 Sum of electronic and thermal Free Energies= -757.364994 PCM-SCFR calculations in acetonitrile: (a.u.) = -757.599089 (a.u.) = -757.665414 Total free energy in solution: with all non electrostatic terms (a.u.) = -757.641352 -------------------------------------------------------------------- (Polarized solute)-Solvent (kcal/mol) = -41.62 -------------------------------------------------------------------- Cavitation energy (kcal/mol) = 26.71 Dispersion energy (kcal/mol) = -12.13 Repulsion energy (kcal/mol) = 0.53 Total non electrostatic (kcal/mol) = 15.10 --------------------------------------------------------------------- Structure (F) Method: B3LYP Basis set: 6-31G(d) HF=-757.606228 (-757.606255) 6 -0.687737 0.182210 0.439712 6 -1.818145 1.160659 0.428268 6 -2.898246 0.580700 -0.588908 6 -3.297991 -0.857499 -0.247791 6 -2.080166 -1.783623 -0.205005 6 -0.995142 -1.238961 0.777062 6 -1.456938 2.571910 0.136653 8 0.458516 0.581743 0.087380 14 2.148376 -0.093864 -0.096886 6 2.621351 -0.705393 1.605005 6 3.054554 1.440668 -0.634675 6 2.021269 -1.407928 -1.421301 1 -3.757524 1.255743 -0.550044 1 -2.298752 1.079973 1.416931 1 -3.820165 -0.880909 0.717864 1 -4.009528 -1.221318 -0.997608 1 -2.352800 -2.791642 0.121388 1 -1.639220 -1.878234 -1.205026 1 -1.407678 -1.261561 1.794840 1 -0.096248 -1.857938 0.761694 1 -2.484284 0.643813 -1.602237 1 -2.165936 3.354459 0.378546 1 -0.566923 2.829061 -0.423167 1 2.990556 2.232863 0.118994 1 2.663547 1.832993 -1.579683 1 4.117207 1.215107 -0.786569 1 2.499668 0.076913 2.362450 1 2.060560 -1.589343 1.925679 1 3.683267 -0.982697 1.597503 1 1.461467 -2.294849 -1.106783 1 1.567370 -1.015922 -2.338333 1 3.033179 -1.742815 -1.683186 Low frequencies --- -9.3695 -3.3661 -2.7776 -0.0028 -0.0023 -0.0018 Sum of electronic and zero-point Energies= -757.327101 Sum of electronic and thermal Energies= -757.310555 Sum of electronic and thermal Enthalpies= -757.309611 Sum of electronic and thermal Free Energies= -757.371889 PCM-SCFR calculations in acetonitrile: (a.u.) = -757.605333 (a.u.) = -757.671221 Total free energy in solution: with all non electrostatic terms (a.u.) = :1 -------------------------------------------------------------------- (Polarized solute)-Solvent (kcal/mol) = -41.34 -------------------------------------------------------------------- Cavitation energy (kcal/mol) = 26.62 Dispersion energy (kcal/mol) = -12.01 Repulsion energy (kcal/mol) = 0.51 Total non electrostatic (kcal/mol) = 15.12