Supporting Information
Mechanism of the Decomposition of Aqueous Hydrogen Peroxide over Heterogeneous TiSBA15 and TS-1 Selective Oxidation Catalysts: Insights from Spectroscopic and DFT Studies.
Chang Won Yoon,‡,1 Kurt F. Hirsekorn,3 Michael L. Neidig,§,3 Xinzheng Yang,1 and T. Don Tilley*,1,2 1
Department of Chemistry, University of California, Berkeley, California 94720, and 2Chemical Sciences Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720 3
‡
The Dow Chemical Company, Core R&D-Chemistry and Catalysis, Midland, MI, 48674
Current address:
The Fuel Cell Center, National Agenda Research Division, Korea Institute of
Science and Technology, Seoul, Korea (ROK). §
Current address: Department of Chemistry, University of Rochester, Rochester, NY 14627
S-1
Ref #71.
Gaussian 03, Revision C.02, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria,
G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, Jr., J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; and Pople, J. A.; Gaussian, Inc., Wallingford CT, 2004.
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Table S1. Nitrogen physisorption and thermal analysis data for TiSBA15 (1) and BucapTiSBA15 (2) materials. SBET % mass Pore Diameter† No. OH sites 2 -1 (m g ) /nm2 loss‡ (nm) 555 4.9 1.9 9.3 TiSBA15 230 4.3 0.16 13 BucapTiSBA15 † ‡ determined from the adsorption isotherm. Determined by TGA at 1000 oC. Material
Table S2. Comparison of geometrical parameters between siloxy-based (HO)Ti[OSi(OH)3]3 (I) and silsesquioxane-based models (I’, Figure S12).
I II
III
Geometrical Parameters Ti-O Ti-O1 Ti-O2 Ti-O3 O1-Ti-O3 Ti-O1 Ti-O2 Ti-O3 O1-Ti-O2 H2-O4 O4-Ti-O2-H2
Siloxy-based model in this study (Å) 1.79 1.90 2.94 2.26 81.08 1.88 2.22 2.30 40.94 2.68 -8.33
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Silsesquioxane-based model (Å) 1.80 1.89 2.93 2.24 81.26 1.91 2.23 2.30 40.64 2.57 -8.41
400
0.06 0.05
350
Volume (mL/g)
Dv (r)
0.04
300
0.03 0.02 0.01
250
0.00 20
40
60
80
100
Pore Diameter (A)
200 150 100 50 0
0.0
0.2
0.4
0.6
0.8
1.0
P / P0
Figure S1.
Nitrogen adsorption-desorption isotherms for TiSBA15 (■, blue), and
BucapTiSBA15 (●, red).
Pore size distributions calculated from the each adsorption isotherm.
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% Weight
100
95
90
85
0
200
400
600
800
1000
Temperature (oC)
Figure S2. TGA data for the TiSBA15 (blue) and BucapTiSBA15 (red).
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(a) TGA 100
(b) DTA 0
BucapTiSBA15
BucapTiSBA15 -5
90 85
H2O desorption
mV
% Weight
95
TiSBA15 -10
80
TiSBA15 75
48 °C
70 20 40 60 80 100 120 140 160 180 200
-15
0
40
80
120
160
200
o
o
Temperature ( C)
Temperature ( C)
Figure S3. TGA (a) and DTA (b) studies following treatment of TiSBA15 and BucapTiSBA15 in a humid environment for ~ 72 h at room temperature.
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F (R) (Normalized)
1.0 0.8 OH
0.6
Ti
O HO
Si O O O
O Si
O O
O
O
0.4 Me Bu Si Me
O
0.2 0.0 200
Bu Ti Me O O Me Si Si Si O O O O O O O O
300
400
500
600
700
Wavelength (nm)
Figure S4. DRUV-vis spectra of TiSBA15 (blue) and BucapTiSBA15 (red).
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Figure S5. DRUV-vis spectra of TS-1 (left) and [Ti,Al]-MFI (right).
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Figure S6.
H2O2 decompositions over TiSBA15 at 65 oC in the presence of 2,6-di-tert-butyl-4-
methylphenol (BHT).
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Figure S7. DRUV-vis spectra of TiSBA15; after exposure in air for several days (blue) and after drying at oven (140 oC) for ~ 20 h (red).
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Figure S8.
A 1H NMR spectrum following dehydration of aqueous H2O2 with Mg(ClO4)2 in
CD2Cl2.
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Figure S9.
DRUV-vis spectra of the reactions of TiSBAS15 with tbutyl hydrogen peroxide
(TBHP) in decane/CH3CN mixture (left).
The DRUV-vis spectrum (right) provides similar
spectral features between TiSBA15 + TBHP and TiSBA15 + dried H2O2.
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Figure S10.
Solid-state 31P MAS NMR spectra of KH2PO4, TiSBA15 following treatment with
KH2PO4, and TiSBA15 following treatment with KH2PO4 + H2O2.
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(b) TiSBA15 + H2O2 + NaHCO3
(a) TiSBA15 + + H2O2 + K2HPO4
1.0
205.8 nm
0.8
F (R) (Normalized)
F (R) (Normalized)
1.0
0.6 0.4
318.2 nm
0.2 0.0 20000
30000
40000
0.6 0.4
0.0 20000
50000
320.5 nm 30000
254.4 nm 40000
50000
Wavenumber (cm-1)
-1
Wavenumber (cm )
Figure S11.
0.8
0.2
255.6 nm
203.3 nm
DRUV-vis spectra of TiSBA15 following treatment of (a) K2HPO4 + H2O2 and (b)
NaHCO3 + H2O2.
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"Validation of Molecular Model I"
Eisenstein and coworkers recently modeled a well-defined, silica-supported olefin metathesis catalyst, [(≡SiO)Re(≡CR)(=CHR)(CH2R)], where (≡SiO)Re represents a Re fragment monopodally connected to a silica support. The silica surface, (≡SiO) was quantum mechanically described using cristobalite and edingtonite for surface models, and the (≡SiO) linkage to the surface was also modeled with molecular ligands of the type X3SiO- (X3SiO is triphenylsiloxy or polyoligomeric silsesquioxane (POSS). These studies found that the geometric and electronic properties of the Re fragment on the silica surface have essentially no differences from those with either the triphenylsiloxy or the silsesquioxane ligands. (New J. Chem. 2006, 30, 842-850). These results suggest that Ti molecules possessing siloxy ligands can be utilized to describe the nature of a Ti active center, tripodally connected to the silica surface in TiSBA15 materials, and a model possessing a silsesquioxane moiety can further be employed to validate our siloxy-based molecular model (HO)Ti[OSi(OH)3]3 (I) in this study. In this regard, Ti-silsesquioxane based molecular models (I’, II’, III’ and IV’) were designed and optimized at the same level of theory, B3LYP/6-31+G(d,p). The calculated relative energies of the Ti-silsesquioxane-based molecules, presented in Figure S12, are very similar to those obtained for (HO)Ti[OSi(OH)3]3 (I, Figure 8 in the manuscript), supporting the validity of the siloxy-based molecular model (HO)Ti[OSi(OH)3]3 (I).
In addition, the calculated bond lengths, bond angles, and dihedral
angles are nearly identical for the siloxy- and silsesquioxane-based models, again confirming the efficacy of molecular model I. The calculated geometrical parameters derived from the two models are compared in Table S2.
Figure S12.
The relative energies (in kcal/mol) of I’, II’, and III’ calculated at B3LYP/6-
311+G(d,p).
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Further validation was carried out by examining the oxidation capabilities of Ti(η1OOH) species derived from either the siloxy-based or silsesquioxane-based models using ethylene as the substrate (note that this reaction has been studied extensively, by experiment and theory). Ethylene is oxidized by transfer of an electrophilic oxygen atom from a Ti(η1-OOH) species, and the oxidation capabilities of the Ti-based species can thus be evaluated theoretically by calculating activation energies for the electrophilic oxygen transfers. As presented in Figure S13, the calculated activation energy (12.5 kcal/mol) with the silsesquixane model is nearly identical to that (12.7 kcal/mol) derived from the siloxy-based model, again strongly supporting the validity of (HO)Ti[OSi(OH)3]3 (I).
Figure S13. The calculated activation energies for electrophilic oxygen transfer reactions.
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Figure S14. DRUV-vis spectra of TiSBA15 with H2O2 in the presence of inorganic additives: pH dependence of lmax.
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Figure S15.
TDDFT-predicted spectra for I, II, III, and IV.
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Figure S16. An optimized geometry of (HO)Ti(OSiH3)3 at the B3LYP/LANL2DZ level. Cartesian coordinates of this molecule are presented below.
--------------------------------------------------------------------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------1 22 0 -0.000997 -0.029448 0.506200 2 8 0 -0.036687 0.037861 2.310170 3 8 0 1.459802 -0.934736 -0.029185 4 8 0 -1.458753 -0.899597 -0.094891 5 8 0 0.027360 1.659126 -0.105905 6 14 0 -2.908305 -1.535048 -0.594999 7 1 0 -3.718914 -0.487779 -1.269861 8 1 0 -2.664764 -2.651018 -1.546012 9 1 0 -3.662286 -2.052967 0.577337 10 14 0 0.041869 3.263705 -0.536626 11 1 0 1.165028 3.518741 -1.476104 12 1 0 -1.239031 3.615187 -1.203516 13 1 0 0.213166 4.111589 0.671402 14 14 0 2.871044 -1.601173 -0.596261 15 1 0 2.561980 -2.702867 -1.544721 16 1 0 3.679172 -0.567625 -1.294561 17 1 0 3.656724 -2.146491 0.542115 18 1 0 0.032555 -0.674932 2.956403 ---------------------------------------------------------------- -----
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The
Figure S17.
A DFT optimized transition-state geometry for the process from III to IV.
--------------------------------------------------------------------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------1 22 0 0.172835 -0.507245 1.396763 2 8 0 0.745078 -1.702255 0.101189 3 8 0 -1.824818 -0.314171 0.784388 4 8 0 0.495022 1.223294 0.909214 5 14 0 -2.685573 -0.363989 -0.627817 6 14 0 0.594801 2.494995 -0.117411 7 14 0 1.779031 -1.455268 -1.134103 8 8 0 2.593508 -2.813278 -1.566224 9 1 0 2.166662 -3.636970 -1.302168 10 8 0 0.832048 -0.873334 -2.377782 11 1 0 1.183469 -0.933036 -3.273548 12 8 0 2.926422 -0.345119 -0.684324 13 1 0 2.695779 0.600980 -0.835237 14 8 0 -4.121900 -1.130293 -0.411460 15 1 0 -4.667388 -0.803943 0.312467 16 8 0 -1.967231 -1.146305 -1.856636 17 1 0 -1.017669 -1.020474 -2.038782 18 8 0 -2.919056 1.262686 -0.975791 19 1 0 -3.396681 1.408846 -1.803028 20 8 0 2.108802 2.291829 -0.819341 21 1 0 2.273205 2.844011 -1.593578 22 8 0 0.508247 3.916774 0.708472 23 1 0 0.922300 3.923362 1.578362 24 8 0 -0.488840 2.507481 -1.327493 25 1 0 -1.403000 2.219491 -1.123179 26 8 0 -1.035609 -1.761562 2.412025 27 8 0 -0.338270 -0.693997 3.137050 28 1 0 -1.840779 -1.091535 1.617839 29 8 0 2.274486 -0.599091 1.998189 30 1 0 2.781580 -0.465493 1.159587 31 1 0 2.561430 0.072545 2.631317 ---------------------------------------------------------------------
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Figure S18.
Activation barriers for epoxidation of alkene over Ti-OOH and Ti-OO
intermediates.
All energies (kcal/mol) in the gas phase were calculated at B3LYP/6-
311+G(d,p)//B3LYP/6-31G(d,p).
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Figure S19. DRUV-vis spectrum after treatment of TiSBA15 with K2HPO4 and H2O2 (pH of the solution is ~ 9); experiment (red); each deconvoluted band (dot); a fiited curve based on the deconvoluted bands (solid black).
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F (R) (Normalized)
1.0 0.8 0.6 0.4 0.2 0.0 20000
30000
40000
50000
-1
Wavenumber (cm ) Figure S20.
A DRUV-vis spectrum following treatment of TiSBA15 with K2HPO4; experiment
(green); each deconvoluted band (dot); a fiited curve based on the deconvoluted bands (solid black).
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Figure S21.
The TDDFT-predicted spectrum of VIII.
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Cartesian coordinates for the optimized geometries
I --------------------------------------------------------------------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------------------------------------------------------ --------------1 22 0 -0.008750 -0.000668 1.557019 2 8 0 -0.021159 -0.008291 3.350600 3 8 0 0.747693 1.497763 0.900563 4 8 0 0.946583 -1.374586 0.895630 5 8 0 -1.684949 -0.116729 0.914702 6 14 0 1.780409 -1.935646 -0.412455 7 14 0 -2.581283 -0.565565 -0.395840 8 14 0 0.793534 2.502798 -0.406811 9 1 0 0.698793 -0.008613 3.991569 10 8 0 1.518560 3.926708 -0.031292 11 1 0 2.216253 3.870893 0.630418 12 8 0 1.716270 1.624380 -1.502200 13 1 0 1.856191 2.051954 -2.355765 14 8 0 -0.661282 2.888472 -1.014527 15 1 0 -1.287000 2.155511 -1.186325 16 8 0 2.663150 -3.264479 -0.026738 17 1 0 2.233200 -3.886827 0.569804 18 8 0 2.831959 -0.871896 -1.042388 19 1 0 2.500463 0. 033847 -1.212542 20 8 0 0.547397 -2.314876 -1.487602 21 1 0 0.840080 -2.633295 -2.350128 22 8 0 -2.291651 0.687554 -1.476564 23 1 0 -2.740133 0.607044 -2.327042 24 8 0 -4.173515 -0.663829 -0.013109 25 1 0 -4.469447 -0.052961 0.670531 26 8 0 -2.179320 -2.006919 -1.025987 27 1 0 -1.231035 -2.171249 -1.202147 ---------------------------------------------------------------------
II Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------1 22 0 0.274491 0.427216 1.175021 2 8 0 -0.290670 1.811065 0.167062 3 8 0 1.659287 -0.493027 0.404030 4 8 0 -1.051936 -0.760712 0.911486 5 14 0 2.318426 -0.928999 -1.034838 6 14 0 -1.832570 -2.023894 0.208471 7 14 0 -1.138869 2.149123 -1.204491 8 8 0 -1.360573 3.769789 -1.349964
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9 1 0 -0.714574 4.303313 -0.874108 10 8 0 -0.125047 1.563701 -2.412122 11 1 0 -0.449361 1.689014 -3.312143 12 8 0 -2.615008 1.477972 -1.297523 13 1 0 -2.667934 0.501618 -1.245996 14 8 0 3.905429 -1.330534 -0.855250 15 1 0 4.070030 -2.123796 -0.333834 16 8 0 2.294967 0.243521 -2.159163 17 1 0 1.473229 0.770458 -2.245392 18 8 0 1.429118 -2.274445 -1.507305 19 1 0 1.550362 -2.524226 -2.431623 20 8 0 -2.592705 -1.287011 -1.095559 21 1 0 -3.131062 -1.868437 -1.645364 22 8 0 -2.932930 -2.696615 1.225954 23 1 0 -3.388961 -2.072080 1.800761 24 8 0 -0.857055 -3.235189 -0.261859 25 1 0 -0.022129 -2.963796 -0.694465 26 8 0 1.996797 1.744342 1.797122 27 8 0 -0.017889 0.428150 3.049142 28 8 0 0.668518 1.336284 3.946768 29 1 0 0.802873 0.748493 4.707218 30 1 0 1.906520 1.776680 2.774321 31 1 0 2.791969 1.238466 1.579621 ---------------------------------------------------------------------
III Center Atomic Atomic Coordinat es (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------1 22 0 -0.087607 -0.368366 1.319871 2 8 0 0.182527 -1.716356 0.071046 3 8 0 -1.767496 0.098192 0.777043 4 8 0 0.830390 1.118370 0.844703 5 14 0 -2.672436 0.228069 -0.586598 6 14 0 1.283763 2.342192 -0.152803 7 14 0 1.215011 -1.873518 -1.173000 8 8 0 1.573522 -3.443567 -1.504860 9 1 0 0.997782 -4.080857 -1.066447 10 8 0 0.444238 -1.159324 -2.475517 11 1 0 0.680241 -1.498164 -3.347149 12 8 0 2.645168 -1.112377 -0.842133 13 1 0 2.653174 -0.143123 -1.010828 14 8 0 -4.268014 -0.019105 -0.269650 15 1 0 -4.621088 0.499822 0.461268 16 8 0 -2.320959 -0.817171 -1.783583 17 1 0 -1.387290 -0.942465 -2.035489 18 8 0 -2.406103 1.818789 -1.069786 19 1 0 -2.823337 2.043286 -1.911400 20 8 0 2.492345 1.638773 -1.091438 21 1 0 2.594056 2.042872 -1.962195
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22 8 0 1.907172 3.607283 0.693012 23 1 0 2.736260 3.444378 1.155267 24 8 0 0.103829 2.910619 -1.106094 25 1 0 -0.804466 2.550274 -1.008348 26 8 0 -0.901590 -1.701708 2.890584 27 8 0 -0.357238 -0.371442 3.181941 28 1 0 -1.861707 -1.530785 2.903133 29 8 0 1.995906 -1.141843 1.924658 30 1 0 2.514474 -1.147692 1.091213 31 1 0 2.450944 -0.560952 2.548018 ----------------------------------------------------- ----------------
IV Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------1 22 0 -0.345218 0.122865 1.552502 2 8 0 0.751656 1.235414 0.441262 3 8 0 1.063242 -1.507646 0.851239 4 8 0 -1.652989 -0.785311 0.628342 5 14 0 2.305711 -1.324510 -0.270190 6 14 0 -2.154049 -1.303790 -0.833180 7 14 0 0.466613 2.229391 -0.819471 8 8 0 1.138392 3.721171 -0.688000 9 1 0 0.744972 4.339072 -0.062295 10 8 0 1.199848 1.528294 -2.144263 11 1 0 1.475239 2.131342 -2.844594 12 8 0 -1.166080 2.395298 -1.068846 13 1 0 -1.630903 1.601036 -1.433293 14 8 0 3.136981 -2.731353 -0.179957 15 1 0 4.053390 -2.714631 -0.476505 16 8 0 3.276574 -0.063440 0.108056 17 1 0 2.753123 0.710265 0.378989 18 8 0 1.535272 -1.149403 -1.715683 19 1 0 1.498181 -0.228251 -2.052792 20 8 0 -2.468838 0.121143 -1.680532 21 1 0 -2.930835 -0.016742 -2.516769 22 8 0 -3.588532 -2.106107 -0.786854 23 1 0 -3.513629 -3.064348 -0.714082 24 8 0 -1.088152 -2.254194 -1.625992 25 1 0 -0.161189 -1.953452 -1.700408 26 8 0 0.282011 -0.620516 3.096181 27 8 0 -0.673340 0.439683 3.317953 28 1 0 1.248435 -2.099339 1.593848 29 8 0 -1.763408 1.840339 1.484188 30 1 0 -1.823582 2.157246 0.552289 31 1 0 -2.635345 1.512530 1.743568 ---------------------------------------------------------------------
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V Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------1 22 0 0.171171 0.188202 1.417154 2 8 0 -0.271283 1.788232 0.690605 3 8 0 1.636474 -0.572029 0.624936 4 8 0 -1.183507 -0.879805 0.924927 5 14 0 2.395987 -0.796564 -0.814440 6 14 0 -1.920513 -1.947808 -0.092615 7 14 0 -0.948476 2.421680 -0.667903 8 8 0 -1.107169 4.051050 -0.533768 9 1 0 -0.492997 4.462813 0.083706 10 8 0 0.166670 2.024982 -1.864899 11 1 0 -0.057329 2.347410 -2.746465 12 8 0 -2.427746 1.854123 -1.032304 13 1 0 -2.523998 0.886633 -1.138050 14 8 0 3.943074 -1.310932 -0.591865 15 1 0 4.032928 -2.195275 -0.220137 16 8 0 2.506976 0.546001 -1.721907 17 1 0 1.723196 1.133309 -1.751911 18 8 0 1.489106 -1.994494 -1.569386 19 1 0 1.671711 -2.094702 -2.511831 20 8 0 -2.543086 -0.923907 -1.267594 21 1 0 -2.989807 -1.360696 -2.002558 22 8 0 -3.112838 -2.782125 0.664877 23 1 0 -3.675740 -2.264835 1.251132 24 8 0 -0.920161 -3.062325 -0.717463 25 1 0 -0.040759 -2.743851 -1.007913 26 8 0 1.916760 1.29684 6 2.534831 27 8 0 0.004783 -0.010393 3.240387 28 1 0 1.779434 1.327115 3.493940 29 1 0 2.645197 0.677528 2.371089 ---------------------------------------------------------------------
VI --------------------------------------------------------------------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------1 22 0 0.189478 0.210893 1.426157 2 8 0 -0.376225 1.749429 0.660813 3 8 0 1.652241 -0.530278 0.613455 4 8 0 -1.107139 -0.932065 0.905611 5 14 0 2.440308 -0.688221 -0.817036 6 14 0 -1.807586 -2.019873 -0.105660 7 14 0 -1.091267 2.347025 -0.693111 8 8 0 -1.291494 3.973002 -0.570952 9 1 0 -0.697026 4.398443 0.056795
S-28
10 8 0 0.016553 1.970952 -1.903525 11 1 0 -0.215194 2.300446 -2.780329 12 8 0 -2.558025 1.731684 -1.029467 13 1 0 -2.615950 0.760135 -1.131608 14 8 0 4.026310 -1.061727 -0.581126 15 1 0 4.188474 -1.911117 -0.156162 16 8 0 2.446856 0.656304 -1.729111 17 1 0 1.617287 1.176036 -1.776048 18 8 0 1.645426 -1.963031 -1.570214 19 1 0 1.857439 -2.070528 -2.505519 20 8 0 -2.553038 -1.036536 -1.245677 21 1 0 -2.876960 -1.493241 -2.031095 22 8 0 -2.925560 -2.943056 0.669990 23 1 0 -3.682261 -2.465722 1.027092 24 8 0 -0.768569 -3.066662 -0.783251 25 1 0 0.116357 -2.723337 -1.023608 26 8 0 1.881117 1.521909 2.383590 27 8 0 0.016048 0.015122 3.250062 28 1 0 1.707420 1.287736 3.309590 29 1 0 2.692946 1.057198 2.132959 30 1 0 -0.677429 -0.581101 3.562182 ---------------------------------------------------------------------
VII --------------------------------------------------------------------Center Atomic Atomic Coordinates (Angstroms ) Number Number Type X Y Z --------------------------------------------------------------------1 22 0 -0.229201 0.248500 -0.909172 2 8 0 -2.046116 0.732079 -0.363161 3 8 0 0.468763 1.877966 -0.441564 4 8 0 -0.091524 -0.989004 0.414953 5 8 0 1.366281 -0.444866 -1.728551 6 14 0 -0.378971 -1.588974 1.910784 7 14 0 2.595009 -1.321463 -1.147143 8 14 0 1.451776 2.601767 0.633530 9 8 0 1.222693 4.240480 0.615180 10 1 0 0.325555 4.466217 0.342432 11 8 0 1.006842 1.990934 2.141540 12 1 0 1.572734 2.309985 2.854698 13 8 0 3.051391 2.375803 0.385874 14 1 0 3.276486 1.443096 0.179423 15 8 0 -1.886186 -2.204767 2.031586 16 1 0 -2.546234 -1.771639 1.452684 17 8 0 -0.002651 -0.473333 3.061763 18 1 0 0.254188 0.398739 2.699176 19 8 0 0.688896 -2.865691 2.110488 20 1 0 1.334539 -2.676143 2.800538 21 8 0 3.415429 -0.324533 -0.048213 22 1 0 4.120777 -0.783262 0.422453
S-29
23 8 0 3.637030 -1.720444 -2.379112 24 1 0 3.507221 -1.132509 -3.131657 25 8 0 2.285097 -2.753514 -0.413354 26 1 0 1.651946 -2.752940 0.326925 27 15 0 -3.539502 0.347408 -0.616287 28 8 0 -4.584238 1.380401 -0.395745 29 8 0 -3.564189 -0.380697 -2.040144 30 8 0 -3.820626 -0.908928 0.443862 31 1 0 -4.567848 -0.630964 0.991627 32 8 0 -1.033363 -0.073416 -2.602648 33 1 0 -2.645367 -0.342561 -2.434378 34 1 0 -0.406679 -0.552528 -3.160240 ---------------------------------------------------------------------
VIII --------------------------------------------------------------------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------1 22 0 -0.697484 0.637485 -0.708635 2 8 0 -0.214126 -0.749819 0.376739 3 8 0 1.920548 -1.977938 -1.986711 4 8 0 0.065998 2.207040 -0.116795 5 14 0 3.054461 -1.590677 -0.868827 6 14 0 1.453152 2.757198 0.522536 7 14 0 -0.347856 -1.370086 1.893581 8 8 0 -1.813333 -2.034187 2.182638 9 1 0 -2.570051 -1.671108 1.681953 10 8 0 0.731395 -2.650155 2.028932 11 1 0 0.303660 -3.490395 1.822637 12 8 0 0.081001 -0.231982 2.993182 13 1 0 0.603706 0.504687 2.626518 14 8 0 4.526154 -1.814392 -1.594156 15 1 0 4.409436 -2.084656 -2.511669 16 8 0 3.054765 -2.501501 0.489550 17 1 0 2.230764 -2.557952 1.015159 18 8 0 2.919203 0.024088 -0.435111 19 1 0 2.759521 0.160987 0.510415 20 8 0 1.816985 1.723818 1.805448 21 1 0 2.447042 2.098526 2.433242 22 8 0 1.325409 4.255884 1.205195 23 1 0 1.315290 4.978754 0.568019 24 8 0 2.693804 2.808948 -0.550041 25 1 0 2.918145 1.919271 -0.885271 26 8 0 0.173514 0.154661 -2.274223 27 8 0 -1.262612 0.371586 -2.488372 28 1 0 1.175602 -1.354456 -2.111585 29 8 0 -2.547565 0.768628 -0.170152 30 8 0 -3.478985 -0.981289 -1.759815 31 1 0 -2.643371 -0.689541 -2.201271
S-30
32 15 0 -3.858685 -0.013099 -0.535989 33 8 0 -4.016861 -1.121429 0.688245 34 1 0 -4.827796 -0.900697 1.166647 35 8 0 -5.116994 0.761577 -0.662935 ---------------------------------------------------------------------
TS for III + C2H4 (Figure S17) --------------------------------------------------------------------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------1 22 0 -0.278577 -0.257494 -1.254891 2 8 0 1.415790 0.554743 -1.363473 3 8 0 -1.262201 1.257445 -0.980569 4 8 0 -0.269932 -0.874166 0.472059 5 14 0 -1.449656 2.336330 0.235140 6 14 0 -0.037478 -1.220663 2.048069 7 14 0 2.717416 0.456393 -0.407746 8 8 0 4.057701 1.096982 -1.115319 9 1 0 3.952926 1.301142 -2.051771 10 8 0 2.442814 1.340950 1.004280 11 1 0 3.112118 2.018830 1.164374 12 8 0 2.990255 -1.116382 0.042805 13 1 0 2.657665 -1.316170 0.944059 14 8 0 -2.359735 3.646304 -0.175121 15 1 0 -1.853133 4.397939 -0.502658 16 8 0 -0.015765 2.892554 0.798123 17 1 0 0.766992 2.313404 0.795662 18 8 0 -2.353020 1.559132 1.416460 19 1 0 -2.938284 2.161474 1.892707 20 8 0 1.580274 -1.071990 2.444652 21 1 0 1.850190 -0.145602 2.550572 22 8 0 -0.407842 -2.819394 2.224410 23 1 0 -0.371384 -3.166218 3.122861 24 8 0 -0.903711 -0.218467 3.004973 25 1 0 -1.502661 0.387344 2.519563 26 8 0 -0.717826 -0.483436 -3.195419 27 8 0 -1.668778 -1.423191 -2.010776 28 1 0 -1.442227 0.111000 -3.448954 29 8 0 1.016383 -2.077538 -1.704481 30 1 0 1.794588 -2.027908 -1.108467 31 1 0 0.528126 -2.885364 -1.500452 32 6 0 -2.512390 -2.924419 -0.616720 33 1 0 -1.753378 -3.100020 0.138043 34 1 0 -2.718699 -3.718061 -1.326780 35 6 0 -3.225894 -1.770921 -0.634147 36 1 0 -4.038432 -1.620410 -1.335889 37 1 0 -3.065217 -0.991690 0.102642 ---------------------------------------------------------------------
S-31
TS for IV + C2H4 (Figure S17) --------------------------------------------------------------------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z --------------------------------------------------------------------1 22 0 0.441935 -0.189793 1.322946 2 8 0 -0.284153 -1.447943 0.109052 3 8 0 -1.598888 0.668602 1.515157 4 8 0 1.078994 1.338323 0.505491 5 14 0 -2.866509 0.239613 0.477963 6 14 0 1.053250 2.303693 -0.806996 7 14 0 0.076554 -1.902287 -1.420300 8 8 0 -0.007913 -3.526558 -1.665129 9 1 0 0.828270 -4.002917 -1.620192 10 8 0 -1.160661 -1.231539 -2.330222 11 1 0 -1.295580 -1.613377 -3.205201 12 8 0 1.564127 -1.399224 -1.890735 13 1 0 1.701999 -0.427748 -1.965629 14 8 0 -4.155327 1.051329 1.072376 15 1 0 -5.027499 0.725764 0.824356 16 8 0 -3.141784 -1.371343 0.524298 17 1 0 -2.319739 -1.882219 0.428964 18 8 0 -2.391395 0.786319 -0.997534 19 1 0 -2.062545 0.089767 -1.611389 20 8 0 1.727779 1.339701 -2.006621 21 1 0 1.918101 1.796786 -2.834483 22 8 0 2.033806 3.621 316 -0.702338 23 1 0 1.603544 4.411402 -0.356112 24 8 0 -0.442429 2.843288 -1.188916 25 1 0 -1.187568 2.215888 -1.112998 26 8 0 0.322501 -0.428739 3.021934 27 8 0 1.924568 -0.875494 2.216823 28 1 0 -1.826099 0.749517 2.452562 29 6 0 3.799925 -0.503892 1.447145 30 1 0 4.306148 -0.405928 2.400289 31 1 0 3.624055 0.408287 0.887598 32 6 0 3.500476 -1.722701 0.923481 33 1 0 3.054938 -1.813582 -0.062610 34 1 0 3.717078 -2.635218 1.467821 ---------------------------------------------------------------------
S-32
