The Radical Cation of anti-Tricyclooctadiene and its Rearrangement Products --------------------------------------------------------------------------- T. Bally,* S. Bernhard, S. Matzinger, L. Truttmann, J.-L. Roulin, Z. Zhu, A. Marcinek, J. Gebicki, F. Williams, G.-F- Chen, H. D. Roth, T. Herbertz SUPPORTING INFORMATION ====================== A.) B3LYP/6-31G* optimized geometries, energies, and thermal corrections, as well as RCCSD(T)/cc-pVDZ single-point energies (where calculated) of all the stationary points discussed in this paper) [The results of the CASSCF/CASPT2-calculations on anti-TOD follow at the end of this file] A1. anti-TOD radical cation, 2Ag state ************************************** E (UB3LYP) =-309.2133433, S**2 = 0.752 E (CCSD(T) =-308.3257289 Point group: C2h State=2-AG Program: Gaussian94, Molpro 96.4 ---------------------------------------------- Atomic Coordinates (Angstroms) Number X Y Z ---------------------------------------------- 6 -0.429698 0.691323 0.793064 6 -0.429698 0.691323 -0.793064 6 0.429698 -0.691323 -0.793064 6 0.429698 -0.691323 0.793064 6 0.429698 1.896024 0.688715 6 0.429698 1.896024 -0.688715 6 -0.429698 -1.896024 -0.688715 6 -0.429698 -1.896024 0.688715 1 -1.305408 0.704974 1.443034 1 -1.305408 0.704974 -1.443034 1 1.305408 -0.704974 -1.443034 1 1.305408 -0.704974 1.443034 1 0.86528 1 2.556358 1.433276 1 0.86528 1 2.556358 -1.433276 1 -0.865281 -2.556358 -1.433276 1 -0.865281 -2.556358 1.433276 ---------------------------------------------- nuclear repulsion energy= 341.08221 Zero-point correction= 0.130794 Thermal correction to Energy= 0.137192 Thermal correction to Enthalpy= 0.138136 Thermal correction to Gibbs Free Energy= 0.100791 A2. TS1 : anti-TOD -> BOT*(2A') ******************************* E (UB3LYP) =-309.2020362, S**2 = 0.752 E (CCSD(T) =-308.3194528 Point group: Cs State=2-A' Program: Gaussian94, Molpro 96.4 ---------------------------------------------- Atomic Coordinates (Angstroms) Number X Y Z ---------------------------------------------- 6 -0.436712 0.647695 0.789289 6 -0.436712 0.647695 -0.789289 6 0.360482 -0.638489 0.989606 6 0.360482 1.93041 1 0.670407 1 -1.389144 0.648624 1.330889 6 0.360482 -0.638489 -0.989606 6 0.360482 1.930411 -0.670407 6 -0.308904 -1.916679 0.676395 1 -1.389144 0.648624 -1.330889 1 1.291467 -0.634915 1.560636 1 0.794844 2.568280 1.433283 6 -0.308904 -1.916679 -0.676395 1 1.291467 -0.634915 -1.560636 1 0.794844 2.568280 -1.433283 1 -0.549252 -2.719618 1.369538 1 -0.549252 -2.719618 -1.369538 ---------------------------------------------- Low frequencies --- -18.2622 nuclear repulsion energy= 338.81472 Zero-point correction= 0.128629 Thermal correction to Energy= 0.134932 Thermal correction to Enthalpy= 0.135876 Thermal correction to Gibbs Free Energy= 0.098043 A3. Bifurcation point between TS1 and BOT*(2A') ************************************************ E (UB3LYP) =-309.2007753, S**2 = 0.756 E (CCSD(T) = (not calculated) Poin group: Cs State: 2Ać Program: Gaussian96 ---------------------------------------------- Atomic Coordinates (Angstroms) Number X Y Z ---------------------------------------------- 6 -0.466688 0.610179 0.785690 6 -0.466688 0.610179 -0.785690 6 0.310812 -0.60578 1 1.172410 6 0.310812 1.921439 0.666600 1 -1.432378 0.666949 1.312630 6 0.310812 -0.605781 -1.172410 6 0.310812 1.921439 -0.666600 6 -0.151208 -1.91624 1 0.671240 1 -1.432378 0.666949 -1.312630 1 1.096322 -0.55230 1 1.927550 1 0.689002 2.584029 1.438020 6 -0.151208 -1.916241 -0.671240 1 1.096322 -0.552301 -1.927550 1 0.689002 2.584029 -1.438020 1 -0.375318 -2.75626 1 1.326000 1 -0.375318 -2.756261 -1.326000 ---------------------------------------------- Low frequencies --- -237.1221 -138.9058 Low frequencies --- -28.8244 -21.8842 -0.0090 Low frequencies --- 0.0019 0.0039 23.8758 ****** 2 imaginary frequencies (negative signs) ****** nuclear repulsion energy= 338.81472 No thermal corrections calculated A4. BOT radical cation ********************** E (UB3LYP) =-309.2917165, S**2 = 0.759 E (CCSD(T) =-308.4020030 Point group: Cs State=2-A" Program: Gaussian94, Molpro 96.4 ---------------------------------------------- Atomic Coordinates (Angstroms) Number X Y Z ---------------------------------------------- 6 -0.359734 0.796867 0.781118 6 -0.359734 0.796867 -0.781118 6 -0.359734 -0.526088 1.430745 6 -0.359734 -0.526088 -1.430745 6 -0.330130 -1.711441 0.707920 6 -0.330130 -1.711441 -0.707920 6 1.052049 1.435417 0.666076 6 1.052049 1.435417 -0.666076 1 -1.087796 1.475950 1.245223 1 -1.087796 1.475950 -1.245223 1 1.728091 1.782543 1.440142 1 1.728091 1.782543 -1.440142 1 -0.350289 -0.566730 2.518300 1 -0.350289 -0.566730 -2.518300 1 -0.304706 -2.660292 1.235879 1 -0.304706 -2.660292 -1.235879 ----------------------------------------------- nuclear repulsion energy= 335.65571 Zero-point correction= 0.132663 Thermal correction to Energy= 0.139057 Thermal correction to Enthalpy= 0.140002 Thermal correction to Gibbs Free Energy= 0.101796 A5. TS2: BOT -> anti-BOD ************************* E (UB3LYP) =-309.224240756, S**2 = 0.7799 E (CCSD(T) = (not calculated) Point group: C1 Program: Gaussian94, Molpro 96.4 ---------------------------------------------- Atomic Coordinates (Angstroms) Number X Y Z ---------------------------------------------- 6 0.875668 -0.961924 0.515590 6 0.325453 0.866042 0.332126 6 -0.209781 -1.122123 -0.353649 6 2.105944 -0.362514 -0.084972 1 0.804260 -1.278799 1.557275 6 -1.054133 1.299062 -0.007587 6 1.666667 0.876644 -0.361735 6 -1.637412 -1.013927 -0.070435 1 0.453025 0.994283 1.416839 1 0.047796 -1.158016 -1.417958 1 3.078117 -0.825166 -0.208150 6 -2.04626 6 0.322872 -0.001188 1 -1.267817 2.364901 -0.024884 1 2.150119 1.725812 -0.834251 1 -2.322544 -1.831284 -0.273724 1 -3.099789 0.583472 -0.024031 nuclear repulsion energy= 334.03600 Zero-point correction= 0.129164 Thermal correction to Energy= 0.135462 Thermal correction to Enthalpy= 0.136406 Thermal correction to Gibbs Free Energy= 0.098617 A6. anti-BOD radical cation **************************** E (UB3LYP) =-309.2713253, S**2 = 0.779 E (CCSD(T) =-308.3819310 Point group: C2h State=2-AU Program: Gaussian94, Molpro 96.4 ---------------------------------------------- Atomic Coordinates (Angstroms) Number X Y Z ---------------------------------------------- 6 .000000 1.161895 1.409009 6 .219563 -.743806 .000000 6 -.219563 .743806 .000000 6 .000000 .000000 2.193974 1 .040976 2.178471 1.783951 6 .000000 -1.161895 -1.409009 6 .000000 -1.161895 1.409009 6 .000000 1.161895 -1.409009 1 1.330560 -.682280 .000000 1 -1.330560 .68228 .000000 1 .000000 .000000 3.278240 6 .000000 .000000 -2.193974 1 -.040976 -2.178471 -1.783951 1 -.040976 -2.178471 1.783951 1 .040976 2.178471 -1.783951 1 .000000 .000000 -3.278240 ---------------------------------------------- nuclear repulsion energy= 335.18760 Zero-point correction= .131633 Thermal correction to Energy= .137560 Thermal correction to Enthalpy= .138504 Thermal correction to Gibbs Free Energy= .102071 A7. TS3 : anti-BOD -> 1,3a-DHP (hydrogen shift) *********************************************** E (UB3LYP) =-309.2608825, S**2 = 0.781 E (CCSD(T) =-308.3765784 Point group: C1 Program: Gaussian94, Molpro 96.4 ----------------------------------------------- Atomic Coordinates (Angstroms) Number X Y Z ----------------------------------------------- 6 -1.352472 1.173902 .019630 6 .023172 .745102 .102858 6 -2.182114 -.008269 -.099886 1 -1.694227 2.203144 -.035133 6 -.004828 -.759253 .277050 6 -1.418806 -1.142446 -.054467 6 1.417733 1.152759 .081886 1 -.342365 .984714 -1.030382 1 -3.256644 .035652 -.228715 6 1.386541 -1.164739 -.137435 1 .008635 -.896950 1.380924 6 2.178702 -.019286 -.118327 1 -1.787858 -2.158835 -.126052 1 1.793210 2.168320 .106491 1 1.734577 -2.182395 -.264055 1 3.257100 -.020276 -.230939 ----------------------------------------------- Low frequencies -- -835.1618 nuclear repulsion energy= 336.31096 Zero-point correction= .129049 Thermal correction to Energy= .134726 Thermal correction to Enthalpy= .135671 Thermal correction to Gibbs Free Energy= .098978 A8. 1,3a-dihydropentalene (1,3a-DHP) ************************************ E (UB3LYP) =-309.3138288, S**2 = 0.762 E (CCSD(T) =-308.4280602 Point group: C1 Program: Gaussian94, Molpro 96.4 ----------------------------------------------- Atomic Coordinates (Angstroms) Number X Y Z ----------------------------------------------- 6 -1.393625 1.168646 .086197 6 .005760 .711148 .286905 6 -2.048942 -.148211 -.328660 1 -1.477830 1.979566 -.647119 6 .062145 -.780311 .481249 6 -1.252406 -1.210826 -.157731 6 1.270737 1.199761 -.061809 1 -1.831297 1.557242 1.024092 1 -3.070230 -.181987 -.692930 6 1.436229 -1.097049 -.040538 1 .061509 -1.045998 1.556941 6 2.135589 .095389 -.251046 1 -1.511435 -2.246330 -.343892 1 1.526583 2.237502 -.247224 1 1.836805 -2.096504 -.176567 1 3.172973 .165232 -.560705 ----------------------------------------------- nuclear repulsion energy= 335.25902 Zero-point correction= .133145 Thermal correction to Energy= .139301 Thermal correction to Enthalpy= .140245 Thermal correction to Gibbs Free Energy= .102459 A9. TS4: 1,3a-DHP -> 1,4DHP (hydrogen shift) ******************************************** E (UB3LYP) =-309.2886229, S**2 = 0.767 E (CCSD(T) =-308.4029132 Point group: C1 Program: Gaussian94, Molpro 96.4 ----------------------------------------------- Atomic Coordinates (Angstroms) Number X Y Z ----------------------------------------------- 6 -1.401854 1.192216 .052429 6 .023398 .728747 .072498 6 -2.139047 -.131153 -.093305 1 -1.610038 1.877237 -.779870 6 .045915 -.755689 .104894 6 -1.324407 -1.219840 -.069057 6 1.325014 1.199083 -.047393 1 -1.696326 1.725120 .968494 1 -3.215127 -.180136 -.225753 6 1.424588 -1.141623 -.042852 1 .592390 -1.136587 1.158065 6 2.186634 .089135 -.083044 1 -1.634816 -2.253974 -.153847 1 1.643061 2.233598 -.087205 1 1.810832 -2.152623 -.106957 1 3.268579 .122107 -.137952 ----------------------------------------------- Low frequencies -- -1115.1861 nuclear repulsion energy= 335.35916 Zero-point correction= .129814 Thermal correction to Energy= .135627 Thermal correction to Enthalpy= .136571 Thermal correction to Gibbs Free Energy= .099528 A10. 1,4-dihydropentalene (1,4-DHP) *********************************** E (UB3LYP) =-309.3553783, S**2 = 0.774 E (CCSD(T) =-308.4637527 Point group: C2h State: 2Au Program: Gaussian94, Molpro 96.4 ----------------------------------------------- Atomic Coordinates (Angstroms) Number X Y Z ----------------------------------------------- 6 1.367926 1.253508 .000000 6 -.025442 .706549 .000000 6 2.180725 -.016989 .000000 1 1.584761 1.881198 .876798 6 .025442 -.706549 .000000 6 1.367926 -1.141022 .000000 6 -1.367926 1.141022 .000000 1 1.584761 1.881198 -.876798 1 3.265604 -.030468 .000000 6 -1.367926 -1.253508 .000000 1 -1.584761 -1.881198 -.876798 6 -2.180725 .016989 .000000 1 1.715970 -2.167379 .000000 1 -1.715970 2.167379 .000000 1 -1.584761 -1.881198 .876798 1 -3.265604 .030468 .000000 ----------------------------------------------- nuclear repulsion energy= 333.93713 Zero-point correction= .133859 Thermal correction to Energy= .139963 Thermal correction to Enthalpy= .140907 Thermal correction to Gibbs Free Energy= .103972 A11. TS : BCB -> anti-TOD ************************** UHF: Energy =-309.1954147 S**2=0.775 Frequencies -- -288.4714 Point group: C1 Program: Gaussian94 ----------------------------------------------- Atomic Coordinates (Angstroms) Number X Y Z ----------------------------------------------- 6 -0.655324 0.749260 -0.198400 6 0.747365 0.715392 0.388583 6 -1.873204 0.379251 0.649020 6 -1.185075 -0.551309 -0.784443 1 -0.855367 1.615846 -0.833313 6 -2.476522 -0.464602 -0.265631 6 1.885658 0.561941 -0.635570 6 1.241544 -0.664925 0.861766 1 0.885555 1.543849 1.095313 1 -2.009944 0.443966 1.729518 1 -0.627015 -1.417298 -1.135892 6 2.255953 -0.672454 -0.105020 1 -3.374721 -1.067255 -0.297370 1 2.272239 1.216092 -1.408413 1 1.007795 -1.285250 1.720437 1 3.059086 -1.365277 -0.332109 ----------------------------------------------- Zero-point correction= 0.128567 Thermal correction to Energy= 0.135312 Thermal correction to Enthalpy= 0.136256 Thermal correction to Gibbs Free Energy= 0.097032 ============================================================ B.) Result of CASSCF/ASPT2-calculation on anti- bicyclo[3.3.0]octadiene radical cation (anti-BOD) ************************************************ Geometry: B3LYP/6-31G* opt in C2h Basis: ANO-S, [3s2p1d] on C, [2s] on H Active space: 13 electrons in 12 Orbitals | Ag Bu Au Bg ------------------+------------------- Frozen Orbitals | 3 2 2 1 (only in CASPT2) Inactive Orbitals | 7 5 6 3 Active Orbitals | 4 4 1 3 Orbitals 8-11 of Symmetry Ag are active Orbitals 6-9 of Symmetry Bu are active Orbital 7 of Symmetry Au is active Orbitals 4-6 of Symmetry Bg are active State averagng: the lowest two States of Ag, Au, and Bu symmetry and the lowest three states of of Bg symmetry were averaged Summary of the calculation: =========================== CAS(13/12) + CASPT2 ---------------------------------------------------------------------------- State CASSCF CASPT2 % w DE (in eV) DE (in nm) osc ---------------------------------------------------------------------------- 1-Au -307.319304 -308.227593 74.2% 1-Ag -307.279845 -308.194320 73.2% 0.91 eV 1369 nm 0.0905 1-Bu -307.227637 -308.138669 73.6% 2.42 eV 512 nm 0.0000 1-Bg -307.209724 -308.122104 72.8% 2.87 eV 432 nm 0.0025 2-Bg -307.186660 -308.107559 66.9% 3.27 eV 380 nm 0.0503 2-Bu -307.178744 -308.093642 72.6% 3.65 eV 340 nm 0.0000 2-Ag -307.166623 -308.073245 71.7% 4.20 eV 295 nm 0.0088 3-Bg -307.133463 -308.065584 71.5% 4.41 eV 281 nm 0.1157 2-Au -307.156937 -308.062708 71.7% 4.49 eV 276 nm 0.0000 ---------------------------------------------------------------------------- CAS(13/12) + PT2 (0.1 a.u. level shift) ---------------------------------------------------------------------------- State CASSCF CASPT2 % w DE (in eV) DE (in nm) osc ---------------------------------------------------------------------------- 1-Au -307.319304 -308.226164 75.9% 1-Ag -307.279845 -308.192552 75.3% 0.91 eV 1356 nm 0.0914 1-Bu -307.227637 -308.137097 75.4% 2.42 eV 512 nm 0.0000 1-Bg -307.209724 -308.120282 75.1% 2.88 eV 430 nm 0.0025 2-Bg -307.186660 -308.104430 74.2% 3.31 eV 374 nm 0.0510 2-Bu -307.178744 -308.092296 74.5% 3.64 eV 340 nm 0.0000 2-Ag -307.166623 -308.071398 75.3% 4.21 eV 294 nm 0.0088 3-Bg -307.133463 -308.063475 73.9% 4.43 eV 280 nm 0.1162 2-Au -307.156937 -308.060703 75.4% 4.50 eV 275 nm 0.0000 ----------------------------------------------------------------------------