SI 1

On the track to silica�supported tungsten oxo metathesis catalysts: input from 17

O solid�state NMR.

Nicolas Merle, Guillaume Girard, Nicolas Popoff, Aimery De Mallmann, Yassine Bouhoute,

Julien Trébosc, Elise Berrier, Jean$François Paul, Christopher P. Nicholas, Iker Del Rosal,

Laurent Maron,* Régis M. Gauvin,* Laurent Delevoye* and Mostafa Taoufik.*

��������������� ����

Table of contents

Fig S1. Raman spectrum of 2 SI2

Procedure for best$fit simulation of 17

O MAS spectra SI2

Fig S2. Simulation of 17

O MAS NMR spectra of 5: Influence of NMR parameters SI3

Effect of Euler angle β SI4

Fig. S3: 17

O MAS NMR simulated spectrum of 5* for different values of β SI4

Fig. S4: Error evaluation on CS SI5

Fig. S5: Error evaluation on �CSA SI5

Fig. S6: Error evaluation on CQ SI6

Fig. S7: Error evaluation on ηCSA SI6

Fig. S8: Error evaluation on ηQ SI7

Fig S9: Experimental and simulated 17

O MAS NMR spectra of 3* SI7

Fig S10: Experimental and simulated 17

O MAS NMR spectra of 6* SI8

Fig S11. Influence of LB on spectra line shape of simulated spectra of 2�calc SI8

Fig. S12. Optimized structures of square pyramidal 4b and 2b�calc compounds. SI9

Fig. S13. CSA tensor orientation on grafted species SI9

Fig. S14. EFG tensors at terminal oxo and siloxide O atoms for monografted compounds SI9

XYZ Structures SI10

� �

SI 2

Figure S1 : Selected region of Raman spectrum of 2

Procedure for best�fit simulation of 17

O MAS spectra

The best$fit simulation of MAS NMR spectra dominated by quadrupolar coupling and chemical

shift anisotropy can be conducted through a systematic process composed of a few steps that are

given hereafter. The 17

O MAS NMR spectrum of 5*, at 18.8 T (conditions given elsewhere) is

chosen to illustrate the proposed approach.

The position of the resonance corresponding to the chemical shift can be distinguished from

spinning sidebands by acquiring two spectra at different spinning speeds. This led here to select

the resonance around 720 ppm as that of chemical shift value, other resonances being spinning

sidebands arising from a modulation of the anisotropic interactions. A more accurate

determination of the isotropic chemical shift is further obtained by adjusting the position of a

resonance (Fig. S2a) such that it coincides with the bottom$left part of the resonance at 730.8

ppm (arrow on Fig. S2.f). Parameters defining the chemical shift anisotropy (ECSA and ηCSA)

enable the total envelop of the spinning sideband pattern to match the experimental data (Fig. S2b

and c). Here, the chemical shift anisotropy ECSA is around $1125 ppm to fit the number of

spinning sidebands and the asymmetry parameter ηCSA is chosen close to 0 in order to reproduce

the dissymmetry of the sideband pattern. Note that the sign of ECSA will favour one side of the

spectrum. The next parameter to fit is the quadrupolar coupling constant CQ (Fig. S2d). Due to

quadrupolar interaction terms not averaged out under magic angle spinning, increasing CQ will

broaden the linewidth of individual sidebands. The CQ value must be set to 5.44 MHz in the case

of compound 5* (Fig. S2d). Finally, the asymmetry parameter ηQ related to the quadrupolar

coupling must be set in order to fit the discontinuities of each sideband. In the present case, it is

set to 0.09 (Fig. S2e). These 5 parameters are sufficient to reproduce with high accuracy the

experimental spectrum of compound 5*. All 17

O spectra presented in the main article have been

fitted using the same procedure. The margin of error has been evaluated by systematically

varying each parameter until the observed discontinuities deviate from the experimental spectrum.

SI 3

Figure S2 : 17O MAS NMR simulated spectra (a$d), best$fit simulation of 5 (e) and experimental spectrum of 5* at

18.8 T. a) isotropic resonance at CS= 730.8 ppm ; b) ECSA= 1125 ppm, η= 1 ; c) ECSA= $1125 ppm, ηCSA= 0.05 ; d)

CQ= 5.44 MHz, ηQ= 1 ; e) CQ= 5.44 MHz, ηQ= 0.09. Specific parameters for SIMPSON simulations are those given

in the experimental section of the article.

SI 4

Effect of Euler angle β

The Euler angles (α, β, γ) describing the relative orientation of the Electric Field Gradient (EFG)

and chemical shift (CS) tensorial frames are also important parameters related to the local

structure around the oxygen sites. They can be determined with high accuracy from a best$fit

simulation of the 17

O NMR spectra acquired in static conditions1 with the disadvantage of facing

low sensitivity of the experiment. In sample spinning conditions,2,3

the sensitivity is much better

and the number of discontinuities still allows for the Euler angles to be determined with good

accuracy. In the present case, it is illustrated with the 17

O MAS NMR spectrum of compound 5*.

The best simulation has been obtained with those quadrupolar and CSA parameters mentioned

above and for relative tensor orientations α, β and γ=0. Here we show the effect of changing the β

angle (Fig. S3), the one corresponding to a rotation about the Z$axis of the EFG tensor with

respect that of the CS tensor. The Z$axis is chosen to correspond to the direction of the largest

eigenvalue of the interaction. This information can be deduced from the DFT calculation of the

NMR parameter and they reveal that both CSA and EFG tensors have their Z$axis along the

W=O chemical bond (See Fig. S8 and S9). From Figure S3, it is clear that a relative tilt of EFG

and CS tensors of an angle larger than 10° leads to clear modifications of individual resonance

shapes (see for example the spinning sideband around 870 ppm). It suggest that both EFG and CS

tensorial frames are (quasi$) collinear.

Figure S3 : 17

O MAS NMR spectrum of 5* (bottom) with SIMPSON simulations for different values of β. The other

quadrupolar and CSA parameters are those reported above (CS= 730.8 ppm, ECSA= $1125 ppm, ηCSA= 0.05, CQ=

5.44 MHz, ηQ= 0.09)

1 D. L. Bryce, K. Eichele, R. E. Wasylishen, ���������. 2003, � , 5085. 2 I. Hung, A. Wong, A.P. Howes, T. Anupold, J. Past, A. Samoson, X. Mo, G. Wu, M.E. Smith, S.P. Brown, R.

Dupree, �������������2007, ���, 246. 3 H. J. Jakobsen, H. Bildsøe, J. Skibsted, M Brorson, I. Hung, Z. Gan, ���������. 2011, ��, 7676.

SI 5

Figure S4: Error evaluation on CS: comparison of the experimental

17O NMR spectrum of 5* (black trace) and of the

SIMPSON simulation at various CS values (red)

Figure S5: Error evaluation on �CSA: comparison of the experimental 17O NMR spectrum of 5* (black trace) and of

the SIMPSON simulation at various �CSA values (red)

SI 6

Figure S6: Error evaluation on CQ comparison of the experimental

17O NMR spectrum of 5* (black trace) and of the

SIMPSON simulation at various CQ values (red)

Figure S7: Error evaluation on ηCSA comparison of the experimental

17O NMR spectrum of 5* (black trace) and of

the SIMPSON simulation at various ηCSA values (red)

SI 7

Figure S8: Error evaluation on ηQ comparison of the experimental

17O NMR spectrum of 5* (black trace) and of the

SIMPSON simulation at various ηQ values (red)

Figure S9 : a) 17

O MAS NMR spectrum of 3* at 18.8 T with b) SIMPSON best$fit simulation. The NMR parameters

for the SIMPSON simulation are CS= 734.5 ppm, ECSA= $1110 ppm, η= 0.07, CQ= 5.1 MHz, ηQ= 0.01.

SI 8

Figure S10 : a) 17

O MAS NMR spectrum of 6* at 18.8 T with b) SIMPSON best$fit simulation. The Oterm and Obridge

NMR parameters for the SIMPSON simulation are respectively: CS= 775 ppm, ECSA= $900 ppm, η= 0.85, CQ= 4.6

MHz, ηQ= 0.85 and CS= 490 ppm, ECSA= $405 ppm, η= 0.8, CQ= 1.0 MHz, ηQ= 0.01

Figure S11 : a)

17O MAS NMR spectrum of 2* (bottom) and SIMPSON simulated spectra at 18.8 T with varying

line broadening (LB). NMR parameters for the SIMPSON simulation are: CS= 758 ppm, ECSA= $1200 ppm, η= 0.07,

CQ= 5.7 MHz, ηQ= 0.17

SI 9

(a) 4b (b) 2b�calc

Figure S12. Optimized structures of square pyramidal 4b and 2b�calc compounds.

2�calc 2b�calc

Figure S13. CSA tensor orientation on grafted species

2�calc 2b�calc

Figure S13. EFG tensors at terminal oxo and siloxide oxygen atoms for monografted compounds

SI 10

XYZ structures:

C model

G= $1566,825275 kcal.mol$1

O $0.423835 0.563122 4.079551

Si $0.491608 0.775965 2.459560

O 0.606501 1.930531 2.010321

Si 1.593069 2.311002 0.744225

O 2.913724 3.030044 1.407873

O $0.145029 $0.655275 1.709236

Si $0.538937 $1.516624 0.354808

O $0.446536 $3.118042 0.678115

O $2.021579 1.260411 2.063465

Si $2.797148 2.197604 0.944651

O $1.786387 3.398524 0.419509

Si $0.708401 3.724398 $0.791018

O $1.099257 2.860804 $2.150272

Si $0.757104 1.418724 $2.884600

O 0.773440 0.934616 $2.496323

Si 1.556029 0.019937 $1.356243

O 2.046239 0.954546 $0.089928

O 0.532025 $1.182137 $0.856813

O $2.080850 $1.137386 $0.121557

Si $2.850075 $0.095565 $1.155315

O $1.858509 0.272195 $2.422325

O 2.933382 $0.619586 $1.986997

O $4.133375 2.858973 1.619384

O $3.299116 1.264726 $0.324865

O 0.820569 3.342864 $0.297177

O $4.180891 $0.804398 $1.812819

O $0.782291 5.323454 $1.130497

O $0.839853 1.621395 $4.506592

H 3.634515 3.200510 0.794387

Si $4.459494 4.279592 2.473018

H $4.942296 $0.852263 $1.227225

Si $0.932235 6.232899 $2.545475

Si $1.885950 1.075969 $5.716048

H 2.798144 $1.283355 $2.669583

Si 0.660980 1.016235 5.293577

Si $1.527313 $4.298775 1.212883

H $0.701822 $5.438199 1.701661

H $2.377532 $3.767788 2.318660

H $2.391632 $4.741076 0.080311

H 0.225393 0.299057 6.524769

H 2.049255 0.613148 4.927299

H 0.597306 2.490282 5.510738

H $1.466839 1.768594 $6.966855

H $1.753677 $0.400652 $5.881180

H $3.296054 1.427423 $5.381373

H $0.797728 7.659499 $2.138296

H 0.145025 5.870771 $3.511942

H $2.268805 6.000877 $3.166012

H $5.715313 4.034326 3.236170

H $3.341252 4.595739 3.408593

H $4.654912 5.405955 1.515244

Complex 3

G = $1193,504307 kcal.mol$1

C 0.283812 0.952443 14.627349

C $0.794854 0.060645 15.274116

C $2.039117 0.064489 14.375684

C $0.242804 $1.364006 15.399408

C $1.111591 0.678623 16.652104

W $2.598124 $0.007294 18.014414

C $4.571412 0.716313 17.794932

C $5.800127 $0.142252 17.422606

C $5.695700 $0.692101 15.995724

C $7.034908 0.775037 17.512840

C $5.967852 $1.300846 18.416311

C $2.215125 $1.002507 19.857902

C $0.870863 $1.663924 20.236406

C $1.040756 $2.270217 21.642392

C $0.514434 $2.787354 19.253940

C 0.260770 $0.628148 20.282019

O $2.839563 $1.475942 17.186657

Cl $2.073447 2.088154 19.190926

H 0.557547 0.568274 13.637803

H $0.071627 1.981365 14.501059

H 1.193185 0.983525 15.238010

H 0.031523 $1.754241 14.412730

H 0.659602 $1.382952 16.022352

H $0.981084 $2.041122 15.835925

H $1.376291 1.739342 16.520901

H $0.204583 0.688491 17.282193

H $6.950967 1.621611 16.822299

H $7.945404 0.221749 17.255404

H $7.161170 1.176833 18.524524

H $6.028712 $0.934878 19.448451

H $6.889824 $1.855262 18.208256

H $5.134472 $2.006731 18.345707

H $5.579815 0.119194 15.267686

H $4.847633 $1.373694 15.892929

H $6.605324 $1.244341 15.734108

H $3.005982 $1.767941 19.863720

H $2.471773 $0.246153 20.611837

H 0.396050 $3.303274 19.579527

H $1.317974 $3.529130 19.190758

H $0.338281 $2.405051 18.244429

H 0.453535 $0.192014 19.296006

H 1.191552 $1.095823 20.622693

H 0.023518 0.195470 20.962827

H $0.111197 $2.751901 21.967318

H $1.295804 $1.501023 22.379591

H $1.832832 $3.027185 21.654737

H $1.787313 $0.288198 13.369174

H $2.818875 $0.590719 14.772807

H $2.452175 1.075789 14.277164

H $4.444080 1.541642 17.070182

H $4.750532 1.209717 18.763763

AHCl

$2760,27528 kcal.mol$1

C 0.055709 $1.113480 13.245218

C $0.306378 $1.752051 14.606515

C 0.850319 $1.616492 15.605228

W 1.566694 $1.805883 11.906165

Cl 2.612437 0.249577 13.262320

C 0.431525 $2.772108 10.365323

C $0.561064 $2.240048 9.301500

C $1.641828 $1.355217 9.936142

C 3.608608 $1.467762 11.221688

C 4.306816 $2.468883 10.254711

C 5.791366 $2.042250 10.237004

O 1.109557 0.602158 10.849265

Si 1.034781 1.873645 9.776861

O 2.203954 1.699023 8.625136

Si 2.482553 2.077226 7.037763

O 1.052573 2.103951 6.211009

Si $0.119738 3.171763 5.744099

O 0.531680 4.681803 5.551852

Si 0.761829 6.068706 6.414454

O 0.660241 7.291737 5.321907

O 1.951195 $3.207171 12.737453

C 0.171227 $1.477450 8.191973

C $1.253920 $3.460760 8.664748

C $1.527991 $0.981539 15.146157

C $0.693176 $3.229702 14.456875

SI 2

C 3.777620 $2.365365 8.820012

C 4.237708 $3.923303 10.740050

O 1.300972 3.248664 10.656183

Si 1.932460 4.774446 10.483763

O 0.751462 5.834743 10.024601

Si $0.663554 5.882402 9.165789

O $1.620916 7.086044 9.748935

O $0.458254 1.888884 9.083992

Si $1.561162 2.975152 8.497757

O $1.318373 3.214448 6.881848

O 2.529827 5.290514 11.912441

Si 3.298651 4.581937 13.246788

O 3.138245 4.743525 9.350597

Si 3.363437 4.984868 7.726594

O 4.863428 5.584228 7.470379

Si 6.102204 6.176904 8.453886

O $1.420788 4.413997 9.304883

O $3.048389 2.343296 8.747736

Si $4.615604 2.964603 8.857365

O $0.403696 6.242182 7.578610

O 2.244604 6.056938 7.153627

O 3.229571 3.549251 6.916963

O 3.457262 0.917657 6.421063

Si 4.632914 0.876087 5.206670

O $0.752583 2.666394 4.324524

Si $0.973410 3.357391 2.797798

H 3.994165 5.693613 13.954836

H $4.776258 4.139766 7.952560

H $4.888788 3.367787 10.267198

H $5.538896 1.868794 8.451120

H 4.224500 1.736835 4.058564

H 4.743173 $0.544140 4.772544

H 6.632355 5.087277 9.323498

H 7.166452 6.663763 7.532813

H $1.679170 7.125714 10.708132

H 5.599147 7.299910 9.297642

H 2.272851 3.966320 14.133521

H 4.281782 3.561308 12.788287

H 0.713320 8.177316 5.693199

H 0.348038 3.664473 2.178340

H $1.788067 4.601576 2.907047

H $1.695979 2.338648 1.985954

H 5.935450 1.347715 5.758409

H $0.724042 $1.405078 12.503390

H 0.035772 $0.025899 13.328499

H $1.289891 0.075998 15.303717

H $2.376150 $1.039180 14.453963

H $1.851417 $1.400486 16.106158

H $1.536025 $3.350500 13.764743

H $1.002506 $3.638153 15.425327

H 0.142240 $3.833879 14.094215

H 0.550828 $2.019009 16.580072

H 1.731730 $2.166590 15.264341

H 1.142045 $0.571166 15.737934

H 3.834458 $1.337766 8.445867

H 2.737033 $2.687256 8.739363

H 4.366797 $3.000552 8.148282

H 3.224455 $4.333135 10.687736

H 4.881895 $4.558087 10.120592

H 4.573168 $4.012699 11.778653

H 5.900729 $1.000217 9.916945

H 6.361646 $2.670425 9.541939

H 6.244327 $2.139238 11.229601

H 4.214083 $1.395620 12.129467

H 3.627815 $0.465572 10.774937

H $0.542478 $1.039896 7.486234

H 0.787408 $0.669292 8.590182

H 0.830138 $2.144082 7.625697

H $0.523742 $4.140266 8.210743

H $1.949301 $3.142920 7.879023

H $1.826106 $4.028059 9.407766

H $2.380463 $1.056658 9.184563

H $2.179539 $1.896408 10.725017

H $1.225866 $0.439424 10.362694

H 1.178865 $3.410778 9.863654

H $0.119061 $3.485933 11.005261

H 1.617942 0.860827 11.667748

TSHCl

$2760,271601 kcal.mol$1

C 0.131554 $0.993581 13.136736

C $0.148966 $1.658224 14.501242

C 1.118527 $1.670728 15.367414

W 1.470966 $1.698887 11.658781

Cl 2.688697 0.907256 13.177194

C 0.329429 $2.769422 10.202299

C $0.640483 $2.217414 9.132483

C $1.706684 $1.316718 9.768732

C 3.543604 $1.367092 11.200330

C 4.339974 $2.348683 10.298986

C 5.798614 $1.844654 10.327309

O 1.183001 0.481683 10.882842

Si 1.077966 1.745190 9.794490

O 2.234246 1.547820 8.632597

Si 2.508657 1.953942 7.049844

O 1.072974 2.000222 6.233092

Si $0.093139 3.083733 5.787300

O 0.567345 4.589199 5.598436

Si 0.826907 5.966770 6.468975

O 0.722094 7.197413 5.385197

O 1.831426 $3.120887 12.476058

C 0.118106 $1.475339 8.027304

C $1.348719 $3.430152 8.496961

C $1.222578 $0.797803 15.196936

C $0.693648 $3.083655 14.341372

C 3.853253 $2.309856 8.844402

C 4.320991 $3.791768 10.819833

O 1.332854 3.126774 10.652883

Si 2.023969 4.628249 10.523431

O 0.850136 5.716877 10.088764

Si $0.567987 5.775115 9.238335

O $1.517438 6.980102 9.833267

O $0.425256 1.764670 9.119489

Si $1.510850 2.883232 8.555193

O $1.279673 3.126830 6.938360

O 2.691234 5.092719 11.932090

Si 2.533245 4.791644 13.593304

O 3.212380 4.600428 9.374675

Si 3.427922 4.852040 7.753741

O 4.929444 5.443115 7.489743

Si 6.270533 5.759140 8.469966

O $1.338671 4.311401 9.372047

O $3.008528 2.276683 8.812987

Si $4.543793 2.946213 9.036655

O $0.321558 6.138327 7.649449

O 2.320355 5.937505 7.184518

O 3.267120 3.418524 6.940361

O 3.468322 0.789877 6.415675

Si 4.554454 0.730965 5.120634

O $0.739949 2.590086 4.369364

Si $1.120336 3.343963 2.904842

H 2.514128 6.132392 14.251566

H $4.718618 4.151970 8.176102

H $4.721029 3.314916 10.471121

H $5.524907 1.892153 8.655752

H 4.079505 1.598872 4.004058

H 4.613347 $0.690401 4.679471

H 6.709949 4.512347 9.160130

H 7.341337 6.245620 7.555693

H $1.544230 7.034667 10.793009

H 5.935676 6.809299 9.474324

SI 3

H 1.253382 4.082000 13.868997

H 3.708729 4.010379 14.054825

H 0.840643 8.077896 5.753516

H 0.128783 3.763441 2.207031

H $1.995036 4.528062 3.143974

H $1.844547 2.325602 2.093797

H 5.899041 1.181997 5.580791

H $0.738647 $1.159836 12.457963

H 0.247064 0.084010 13.263932

H $0.861457 0.221964 15.367216

H $2.139199 $0.739115 14.598246

H $1.486147 $1.229253 16.169475

H $1.615003 $3.091690 13.745334

H $0.933946 $3.507788 15.322602

H 0.034579 $3.744841 13.864540

H 0.882601 $2.040987 16.371900

H 1.883138 $2.324972 14.938648

H 1.545515 $0.667863 15.456901

H 3.871153 $1.292493 8.440499

H 2.831853 $2.688964 8.743570

H 4.492645 $2.934734 8.210163

H 3.333063 $4.253462 10.733180

H 5.025321 $4.405942 10.246982

H 4.613235 $3.838539 11.874202

H 5.868856 $0.809808 9.975470

H 6.429131 $2.465586 9.679617

H 6.211861 $1.884531 11.340738

H 4.019859 $1.312926 12.186300

H 3.614071 $0.358625 10.777044

H $0.576079 $1.058066 7.290799

H 0.715588 $0.649160 8.417848

H 0.798713 $2.151418 7.498526

H $0.628361 $4.120146 8.043386

H $2.037951 $3.101089 7.710652

H $1.930103 $3.987901 9.239673

H $2.434633 $0.990711 9.018775

H $2.256556 $1.856127 10.550110

H $1.274751 $0.413858 10.207283

H 1.079535 $3.417013 9.717985

H $0.234429 $3.451793 10.858527

H 1.744674 0.831825 11.746200

2�calc + HCl

$2760,312479 kcal.mol$1

C $0.018121 $0.581613 12.412016

C $0.515961 $0.935663 13.826160

C 0.650866 $1.003907 14.819566

W 1.218476 $1.805924 11.183945

Cl 6.350755 2.759743 12.030774

C 0.290881 $3.309983 9.993085

C $0.310855 $3.126141 8.582552

C $1.482785 $2.135527 8.600746

C 3.279969 $1.391415 10.873143

C 4.455138 $2.226813 11.417756

C 5.743155 $1.644268 10.802271

O 0.968107 $0.307713 9.880519

Si 0.984538 1.234390 9.372484

O 1.985219 1.405830 8.061616

Si 2.111939 2.268153 6.660969

O 0.613985 2.731689 6.122836

Si $0.435320 4.005133 6.220227

O 0.395674 5.417880 6.454488

Si 0.938043 6.372376 7.686465

O 0.913289 7.910545 7.106954

O 1.525424 $2.923782 12.443019

C 0.757476 $2.675081 7.577365

C $0.844548 $4.504166 8.142233

C $1.472763 0.192459 14.261227

C $1.289527 $2.261691 13.829446

C 4.331535 $3.697939 10.994530

C 4.549346 $2.125616 12.945277

O 1.533472 2.219100 10.601702

Si 2.347478 3.637068 10.804863

O 1.292277 4.901658 10.944372

Si $0.201323 5.362741 10.404450

O $0.824342 6.294626 11.607887

O $0.547438 1.705422 8.945842

Si $1.571172 2.996408 8.930739

O $1.501558 3.759586 7.461159

O 3.225730 3.559841 12.206300

Si 2.876126 4.217212 13.744411

O 3.416008 3.874629 9.575070

Si 3.491262 4.651432 8.111310

O 5.005994 5.204766 7.858990

Si 6.481802 4.518840 7.393879

O $1.176112 4.051629 10.143688

O $3.104235 2.486728 9.197664

Si $4.453718 2.231363 8.214211

O $0.062195 6.226962 9.000264

O 2.474232 5.954089 8.137863

O 3.057155 3.605398 6.905248

O 2.822021 1.325338 5.527368

Si 2.453795 0.889925 3.937935

O $1.273696 4.099895 4.818535

Si $1.539835 5.321074 3.679845

H 3.064886 5.693499 13.710362

H $5.057555 3.541734 7.834311

H $5.419647 1.441932 9.028318

H $4.072951 1.473620 6.987259

H 2.281470 2.108112 3.093691

H 1.207769 0.070878 3.903881

H 6.479362 3.051153 7.653787

H 6.687191 4.780346 5.939878

H $1.757307 6.508406 11.514178

H 7.544764 5.191732 8.189942

H 1.478721 3.873860 14.129641

H 3.849302 3.581828 14.672941

H 1.440385 8.540120 7.607903

H $0.249126 5.736480 3.059457

H $2.197665 6.493662 4.325328

H $2.439222 4.731467 2.648848

H 3.609117 0.087257 3.448647

H $0.884624 $0.434963 11.741957

H 0.501111 0.390266 12.429520

H $0.965101 1.163703 14.271578

H $2.331859 0.270566 13.584910

H $1.856976 0.004457 15.270710

H $2.121400 $2.233806 13.114588

H $1.714461 $2.455266 14.820895

H $0.637818 $3.101217 13.573528

H 0.281972 $1.197638 15.833280

H 1.348283 $1.801513 14.553112

H 1.201806 $0.055791 14.843852

H 4.246999 $3.790038 9.904413

H 3.460077 $4.173023 11.454020

H 5.220126 $4.260418 11.302699

H 3.662254 $2.544658 13.426482

H 5.425286 $2.674057 13.310006

H 4.658043 $1.081704 13.262382

H 5.726292 $1.709893 9.708127

H 6.621305 $2.196627 11.156920

H 5.877177 $0.592050 11.075541

H 3.385597 $0.339730 11.189972

H 3.324207 $1.366164 9.770283

H 0.334282 $2.613515 6.568270

H 1.159440 $1.692038 7.834226

H 1.589134 $3.389354 7.542307

H $0.042811 $5.250713 8.111884

H $1.284458 $4.443900 7.139818

H $1.618905 $4.868944 8.826584

H $1.948904 $2.075016 7.610593

SI 4

H $2.256036 $2.457967 9.308810

H $1.157352 $1.130566 8.879476

H 1.067761 $4.092293 9.959163

H $0.480578 $3.712083 10.670929

H 5.090029 3.070409 12.014019

ACMe4

$2760,316256 kcal.mol$1

C 0.993923 $0.629097 12.924848

W 2.409724 $1.895566 11.997791

C 4.059918 $2.617728 13.124298

C 4.328659 $4.089313 13.506019

C 5.668114 $4.117938 14.268188

C $0.168388 $1.075358 13.838024

C 0.371263 $1.841040 15.053406

C $0.869148 0.208358 14.324035

C $1.190366 $1.936671 13.087268

Cl 3.790964 0.137084 11.747488

O $1.155162 0.990723 10.214818

Si $0.711222 2.396788 9.474703

O $2.048812 3.146172 8.841630

Si $2.635316 4.678936 8.599186

O $2.240123 5.209688 7.085691

Si $1.068792 5.010997 5.936534

O 0.108492 6.158967 6.117890

Si 0.804297 7.071385 7.305780

O 2.130573 6.309596 7.939073

Si 2.727433 4.786104 8.166265

O 2.342942 4.249571 9.682199

Si 1.173437 4.448070 10.837211

O 0.518281 5.960970 10.699921

Si $0.747024 6.733202 9.983473

O $1.190223 7.938065 11.011475

O 1.492754 $3.320972 12.166230

C 2.467082 $1.951147 9.877440

C 1.592824 $2.838263 8.965428

C 1.856620 $4.331637 9.188793

O 0.350522 2.075528 8.245682

Si 0.839930 2.710860 6.800212

O 2.101642 3.751926 7.031492

O $0.017873 3.317083 10.645305

O $0.416744 3.495190 6.060252

O 1.330173 1.468395 5.851541

Si 1.152892 1.105982 4.210426

O $1.738607 5.147341 4.450620

Si $1.828348 6.372732 3.290328

O 1.813949 4.255595 12.325197

Si 3.291978 4.591507 13.073069

O $4.267447 4.659070 8.730708

Si $5.415848 3.493269 9.141516

O $2.027866 5.708164 9.739119

O $0.283020 7.359013 8.520288

O 1.247570 8.477616 6.577401

O 4.352926 4.858443 8.004117

Si 5.568717 3.730821 7.673937

C 0.105631 $2.530947 9.188229

C 1.959088 $2.483240 7.510921

C 4.461064 $4.948971 12.241526

C 3.236478 $4.662427 14.415911

H $6.734874 4.184813 9.135791

H $5.131100 2.938331 10.496916

H $5.412578 2.389936 8.136158

H 1.435722 2.309916 3.376242

H $0.231969 0.618712 3.946692

H 5.172723 2.377875 8.157739

H 5.813880 3.697097 6.202713

H $2.022403 8.367815 10.793135

H 6.792556 4.200486 8.381718

H 3.160505 4.127647 14.482076

H 3.545904 6.062786 13.043611

H 4.397379 3.871184 12.383674

H 1.830552 9.037056 7.099163

H $0.510366 6.523485 2.609330

H $2.226479 7.662903 3.924081

H $2.864021 5.940565 2.310299

H 2.138963 0.030636 3.910539

H 0.597784 $0.102940 12.034066

H 1.603576 0.116658 13.454291

H $0.181764 0.847730 14.889345

H $1.253833 0.791194 13.480672

H $1.712718 $0.039154 14.979223

H $1.589899 $1.396489 12.221752

H $2.033042 $2.183398 13.743327

H $0.748219 $2.874043 12.740183

H $0.439862 $2.081188 15.750335

H 0.840308 $2.782492 14.752437

H 1.110952 $1.244349 15.601075

H 5.240654 $4.557423 11.576860

H 3.519357 $4.983120 11.686400

H 4.733492 $5.978402 12.500392

H 2.269078 $4.694731 13.908992

H 3.492844 $5.684060 14.718864

H 3.130851 $4.064235 15.328603

H 6.487715 $3.734307 13.650184

H 5.921481 $5.142994 14.562878

H 5.620820 $3.510319 15.178965

H 3.955588 $1.997777 14.036353

H 4.940652 $2.213804 12.605498

H $0.514193 $3.091694 8.479174

H $0.210470 $2.804031 10.199199

H $0.093588 $1.463434 9.039848

H 1.770969 $1.425325 7.297595

H 1.365624 $3.081215 6.809076

H 3.017202 $2.684369 7.308879

H 1.269986 $4.931111 8.483249

H 2.913807 $4.573319 9.027498

H 1.582272 $4.639681 10.200779

H 2.341479 $0.897684 9.586602

H 3.538517 $2.169864 9.707609

H $1.653279 0.377872 9.665881

TSCMe4

$2760,267156 kcal.mol$1

C 0.986227 0.125404 13.224749

W 1.728173 $1.288706 11.879505

C 3.150990 $2.244057 13.165220

C 3.916574 $3.561434 12.854884

C 4.726576 $3.923296 14.114155

C $0.299464 $0.004231 14.069232

C $0.255541 $1.245945 14.969338

C $0.380203 1.251585 14.958591

C $1.536365 $0.060049 13.163531

Cl 3.644242 $0.021353 11.094224

O 0.485109 0.097856 10.512567

Si 0.510017 1.584760 9.845269

O $1.036344 1.976059 9.372236

Si $2.051158 3.274750 9.284761

O $2.003544 3.918018 7.758920

Si $0.958240 4.070047 6.488897

O $0.142950 5.507093 6.592192

Si 0.392573 6.566349 7.739072

O 1.942876 6.202481 8.193290

Si 2.969442 4.911483 8.285288

O 2.937475 4.285573 9.815816

Si 1.874710 4.117951 11.075836

O 0.824392 5.396635 11.089557

Si $0.685909 5.771417 10.546885

O $1.340776 6.783493 11.667375

O 0.616087 $2.549162 12.117939

C 1.746102 $1.986035 9.570239

C 0.723173 $2.663557 8.619749

SI 5

C $0.392370 $3.388069 9.379054

O 1.491914 1.629832 8.506751

Si 1.604620 2.392492 7.051603

O 2.542096 3.751990 7.181897

O 1.016320 2.715290 10.949283

O 0.108094 2.806542 6.474487

O 2.309207 1.351332 5.997456

Si 2.260318 1.170934 4.319255

O $1.802645 4.029814 5.086938

Si $2.318161 5.193172 3.976420

O 2.707296 4.088130 12.485120

Si 4.245123 4.601538 12.959027

O $3.587317 2.814615 9.623186

Si $4.547048 1.479919 9.242680

O $1.640891 4.426182 10.397358

O $0.583999 6.529273 9.075276

O 0.335425 8.048200 7.026767

O 4.484961 5.437360 7.956611

Si 5.793627 4.808185 7.094727

C 0.106915 $1.626200 7.669320

C 1.519296 $3.686130 7.785924

C 4.895644 $3.370419 11.688893

C 2.951861 $4.714411 12.549943

H $5.955322 1.964095 9.184642

H $4.408679 0.448053 10.310424

H $4.149414 0.902992 7.925067

H 2.345353 2.499900 3.645428

H 1.000647 0.480501 3.918542

H 6.026581 3.382062 7.464267

H 5.536157 4.916744 5.629121

H $2.295984 6.878049 11.607129

H 6.975402 5.635982 7.466003

H 4.292255 4.456227 14.441318

H 4.452228 6.030460 12.580686

H 5.292977 3.751635 12.325849

H 0.701875 8.764079 7.554282

H $1.154406 5.706878 3.197991

H $3.000205 6.319809 4.676982

H $3.275156 4.502169 3.066811

H 3.438172 0.335367 3.951883

H 1.037825 1.101644 12.731377

H 1.877624 0.068631 13.889372

H 0.492085 1.331983 15.617242

H $0.432231 2.163324 14.354554

H $1.274447 1.213644 15.591125

H $1.597525 0.821065 12.518255

H $2.446228 $0.098033 13.773271

H $1.516190 $0.946071 12.523139

H $1.152869 $1.289304 15.596300

H $0.214922 $2.168167 14.383014

H 0.612560 $1.219849 15.639500

H 5.586482 $2.543653 11.881810

H 4.382612 $3.149919 10.747409

H 5.486936 $4.281022 11.538403

H 2.379055 $4.543278 11.633357

H 3.507055 $5.651223 12.425721

H 2.229952 $4.855770 13.361577

H 5.434723 $3.128022 14.371471

H 5.299996 $4.843966 13.954327

H 4.069438 $4.083515 14.976266

H 2.527315 $2.434947 14.055719

H 3.888454 $1.479711 13.439488

H $0.519197 $2.128505 6.923874

H $0.525626 $0.913862 8.206201

H 0.879710 $1.062550 7.136831

H 2.332166 $3.204628 7.231388

H 0.860735 $4.174942 7.058988

H 1.954765 $4.466167 8.420894

H $1.059254 $3.888463 8.667662

H 0.004484 $4.146096 10.060919

H $0.992425 $2.690506 9.970114

H 2.502327 $1.434759 9.002024

H 2.286682 $2.776988 10.114412

H 1.068790 $0.924618 9.990639

4a + CMe4

$2760,370526 kcal.mol$1

C 1.702562 0.866890 14.303938

C 0.265952 0.865491 14.869113

C $0.719257 1.497269 13.875477

W 2.282882 0.039783 12.426140

O 0.847528 $0.872130 12.332832

C 3.475481 $1.722447 12.396955

C 3.047849 $3.061464 11.758780

C 1.927413 $3.746257 12.550148

Cl 4.423674 1.082947 13.045902

O 2.194406 1.023153 10.846234

Si 1.771006 2.456778 10.123203

O 1.628309 3.607689 11.292042

Si 1.899698 5.230176 11.511104

O 2.364622 5.469644 13.057702

Si 3.671865 6.243831 13.804181

C 4.290890 $3.973408 11.779252

C 2.614618 $2.849946 10.300397

C $0.191287 $0.549661 15.243830

C 0.297399 1.727624 16.147062

O 0.326906 2.229008 9.359125

Si $1.027003 3.106675 8.963516

O $1.270002 4.305222 10.073081

Si $0.893346 5.896341 10.345436

O $0.727719 6.667898 8.888433

Si 0.444991 7.069609 7.790842

O 0.042973 8.452704 6.998064

O 2.956417 2.822784 9.042994

Si 3.136286 3.610842 7.593067

O 4.383108 2.954257 6.765982

Si 4.688405 1.459202 6.039164

O $0.846592 3.752753 7.453211

Si 0.331855 4.286509 6.424128

O $0.132257 3.985208 4.885875

Si $0.497204 4.941579 3.540433

O $2.338825 2.132414 8.991410

Si $2.641481 0.507585 8.633055

O 0.571025 5.912357 6.620682

O 1.737243 3.466886 6.723122

O 1.884252 7.254777 8.588996

Si 3.246954 6.401543 8.967802

O 4.525899 7.419694 8.967018

Si 6.042859 7.435186 8.220700

O 3.086478 5.747884 10.479913

O 3.497543 5.200237 7.854383

O 0.495878 6.049043 11.221397

O $2.082704 6.595997 11.239253

C $0.787739 $6.948717 8.583836

C $1.643532 $6.218156 7.539600

C $2.192435 $7.233199 6.527266

C $0.781384 $5.180354 6.807332

C $2.811744 $5.510380 8.240236

H $4.079071 0.418682 8.253205

H $2.375296 $0.323254 9.841281

H $1.780555 0.056658 7.501027

H 4.549082 1.608940 4.562518

H 3.729510 0.432154 6.540973

H 6.785915 6.181368 8.535596

H 5.884125 7.578457 6.744637

H $2.975277 6.334166 10.994822

H 6.762713 8.615179 8.775821

H 3.464091 6.078262 15.269360

H 3.671640 7.692384 13.446213

H 4.954529 5.613084 13.384250

H 0.007353 9.240977 7.548004

SI 6

H 0.712848 5.696394 3.104548

H $1.601833 5.889068 3.865339

H $0.926315 3.998206 2.470304

H 6.085254 1.075531 6.386177

H 2.079949 1.898348 14.247825

H 2.388322 0.354698 15.002899

H 1.001877 1.323993 16.883222

H 0.594742 2.758302 15.924345

H $0.694036 1.757572 16.613567

H $0.393770 2.500920 13.579160

H $1.712657 1.591333 14.328394

H $0.822736 0.886017 12.974448

H $1.189352 $0.520144 15.695515

H $0.237510 $1.201895 14.368715

H 0.488999 $1.000620 15.976610

H 3.397671 $2.343810 9.723473

H 1.700310 $2.252054 10.238161

H 2.416258 $3.812550 9.815983

H 1.013996 $3.147857 12.557601

H 1.691157 $4.719590 12.105390

H 2.232224 $3.923447 13.588506

H 5.113721 $3.540583 11.199220

H 4.055073 $4.953359 11.348650

H 4.648545 $4.134818 12.802414

H 3.675050 $1.852578 13.478001

H 4.430041 $1.394810 11.966121

H $3.447021 $6.227457 8.772828

H $2.450133 $4.778421 8.971877

H $3.442044 $4.978271 7.518275

H $2.809312 $6.740157 5.767100

H $2.813209 $7.989251 7.021707

H $1.379169 $7.755193 6.010030

H $1.376731 $7.699007 9.123823

H 0.057268 $7.463993 8.112631

H $0.381993 $6.248267 9.322979

H $1.365729 $4.641920 6.052227

H 0.063747 $5.656748 6.297101

H $0.374926 $4.439494 7.505617

2�calc

G = $2299,563038 kcal.mol$1

C $0.060725 $0.681301 12.733346

C $0.794014 $1.017125 14.046189

C 0.142925 $0.868341 15.252216

W 1.593350 $1.743466 11.933488

C 1.222909 $3.413464 10.646204

C 0.634643 $3.379191 9.217684

C $0.690636 $2.604493 9.180827

O 1.507629 $0.422525 10.442259

Si 1.373746 1.064934 9.797533

O 1.901666 2.190271 10.900036

Si 2.645535 3.659249 10.974284

O 1.521849 4.874725 11.059141

Si $0.027391 5.194534 10.562687

O $0.871332 3.772057 10.489032

Si $1.302201 2.610815 9.392013

O $2.780802 2.036249 9.799750

Si $4.260641 1.906466 8.995663

O 2.281442 1.180746 8.414221

Si 2.265145 1.938328 6.948617

O 2.976630 0.965008 5.840964

Si 2.500981 0.304837 4.361620

O 0.709782 2.255111 6.470494

Si $0.411099 3.468569 6.541404

O $1.374488 3.264882 7.870614

O $1.341956 3.394713 5.198136

Si $1.770260 4.491869 3.985728

O 0.344229 4.939475 6.606502

Si 0.875798 6.039755 7.715990

O $0.022499 5.966774 9.105577

O 3.128163 3.348170 7.035012

Si 3.552998 4.517297 8.128610

O 3.615797 3.883042 9.653465

O $0.216008 1.370897 9.428737

O 2.463478 5.759776 8.090312

O 0.690202 7.509543 7.003550

O 5.031927 5.104319 7.744951

Si 6.182341 4.735795 6.564542

O $0.757102 6.234094 11.608811

O 3.561292 3.672110 12.332904

Si 4.337315 4.867386 13.238052

C 3.534832 $0.950079 12.351043

C 4.831503 $1.700887 11.973501

C 6.015999 $0.830904 12.435431

C $1.951618 $0.009321 14.189522

C $1.378727 $2.435778 14.006411

C 4.924511 $1.887106 10.451971

C 4.919127 $3.063850 12.673414

C 1.623440 $2.790857 8.203812

C 0.351160 $4.843173 8.822366

H 0.870682 8.262826 7.573638

H $1.012111 5.846881 12.451346

H $5.183968 1.215585 9.938978

H $4.788337 3.261864 8.664211

H $4.105495 1.102611 7.748853

H $2.694799 3.758112 3.076471

H $2.462005 5.672903 4.577691

H $0.557110 4.931163 3.237918

H 4.803824 5.975493 12.354417

H 3.393826 5.401223 14.263388

H 5.498739 4.216630 13.906257

H 5.626103 4.991738 5.204224

H 7.341219 5.636120 6.821006

H 6.604019 3.309754 6.680419

H 1.300905 $0.562288 4.540637

H 2.197803 1.392269 3.385745

H 3.653437 $0.506544 3.879376

H $0.773242 $0.708321 11.890084

H 0.307402 0.358649 12.770057

H $1.579700 1.021097 14.227337

H $2.651692 $0.081956 13.349426

H $2.513633 $0.196552 15.112053

H $2.048347 $2.562029 13.146717

H $1.963962 $2.634590 14.911417

H $0.587262 $3.187357 13.944927

H $0.404289 $1.039173 16.186286

H 0.964288 $1.587704 15.203438

H 0.567121 0.142339 15.297865

H 4.848216 $0.929208 9.926687

H 4.128452 $2.536924 10.072413

H 5.880752 $2.347281 10.177657

H 4.118652 $3.739763 12.357984

H 5.877291 $3.546222 12.447977

H 4.841365 $2.956406 13.760463

H 5.997609 0.152986 11.954073

H 6.968652 $1.311802 12.183190

H 5.994444 $0.676864 13.519901

H 3.499624 $0.812915 13.442003

H 3.543135 0.043266 11.887295

H 1.194601 $2.817220 7.195335

H 1.876722 $1.755342 8.438531

H 2.551914 $3.373889 8.179823

H 1.264763 $5.447647 8.852774

H $0.051596 $4.895042 7.803910

H $0.380365 $5.304260 9.495811

H $1.153018 $2.681499 8.190011

H $1.404305 $3.010443 9.908342

H $0.542608 $1.543127 9.395917

H 2.195507 $3.936797 10.636146

H 0.575374 $4.038682 11.278882

O 1.736662 $2.803263 13.272183

SI 7

2b�calc

G =$2299,541666 kcal.mol$1

W 1.611753 $2.050327 11.248670

O 0.666044 $0.670299 10.326630

Si 0.695633 0.869427 9.728337

O 1.531134 1.809928 10.798798

O $0.861041 1.396698 9.584353

Si 2.522749 3.135841 10.843551

O 1.444839 0.865715 8.258239

O 3.358766 3.259384 9.420095

O 3.572729 2.966270 12.084614

Si 5.234306 2.668544 12.208032

Si $4.740880 2.279983 9.553637

O 1.618192 4.493735 11.104551

O $0.965358 3.813459 10.773154

Si 0.097924 5.081242 10.805216

O 0.060896 5.915005 9.380823

Si 0.799783 5.924995 7.899976

O 0.000990 4.968545 6.818075

Si $0.997154 3.647158 6.790741

O $0.102538 2.277856 6.554218

Si 3.232275 3.982867 7.937817

O $1.830675 3.529915 8.214130

O 2.507458 2.946075 6.873615

Si 5.516952 5.722606 6.854418

O 4.737848 4.324935 7.397361

O 1.824169 0.676324 5.615361

Si 3.104667 0.582519 4.515861

C 1.187608 $1.065112 13.119255

C $0.258573 $0.880550 13.680811

C $1.330952 $1.580195 12.824135

C 0.886007 $3.649168 9.969635

C 0.898541 $3.471939 8.422661

C 0.800390 $4.883012 7.809875

C 1.327435 $3.791081 12.661320

C 2.571406 $4.580650 13.175496

C 3.358661 $5.248872 12.039881

O 3.301304 $2.041480 11.157176

O $0.327436 6.174788 11.956717

Si $1.719641 2.808916 9.700224

O $3.219219 2.482285 10.262712

Si 1.419616 1.697324 6.825554

O $2.083077 3.803268 5.579357

Si $2.213731 4.770699 4.199774

O 2.358456 5.383854 8.060506

O 0.781724 7.454396 7.297086

C $0.338951 $1.420923 15.118305

C $0.580548 0.623644 13.716591

C $0.310304 $2.660195 7.941330

C 2.202444 $2.823750 7.930886

C 2.040018 $5.691809 14.103890

C 3.521776 $3.693613 13.991899

H 0.793387 8.144688 7.966819

H $0.386823 5.824376 12.850480

H $5.291657 3.606944 9.154483

H $4.643045 1.388051 8.362213

H $5.605075 1.657653 10.594923

H $3.298266 4.171341 3.373250

H $2.574209 6.163798 4.590306

H $0.928442 4.769723 3.442431

H 5.993638 3.866023 11.743810

H 5.501501 2.422124 13.652165

H 5.609765 1.476746 11.396186

H 4.794036 6.294526 5.681888

H 5.583054 6.731741 7.951192

H 6.890386 5.303818 6.459036

H 2.868222 $0.646652 3.709100

H 3.107206 1.784040 3.631521

H 4.403280 0.483082 5.242007

H 1.602069 $0.081397 12.828137

H 1.859493 $1.450980 13.890326

H 0.131802 1.162857 14.351222

H $0.539568 1.064844 12.715998

H $1.587071 0.795508 14.116676

H $1.354237 $1.176865 11.806338

H $2.326144 $1.425275 13.257276

H $1.164564 $2.661421 12.769843

H $1.336734 $1.251533 15.540179

H $0.140773 $2.496917 15.161956

H 0.389107 $0.919504 15.765896

H 3.003310 $3.236720 14.843365

H 3.954094 $2.897407 13.379388

H 4.348118 $4.290566 14.395934

H 3.775096 $4.511826 11.347302

H 4.194194 $5.830024 12.448109

H 2.726650 $5.943344 11.473329

H 1.489869 $5.270327 14.953267

H 2.864992 $6.292971 14.505688

H 1.363242 $6.366880 13.567654

H 0.660868 $4.524086 12.191261

H 0.797710 $3.449288 13.554055

H 2.236648 $2.819206 6.835259

H 2.293655 $1.782495 8.256622

H 3.079431 $3.372325 8.291792

H 1.668793 $5.494146 8.080659

H 0.756029 $4.828051 6.715298

H $0.099698 $5.403049 8.156823

H $0.304898 $2.572784 6.848862

H $1.248158 $3.148326 8.231864

H $0.315985 $1.650568 8.355958

H 1.508260 $4.517375 10.213266

H $0.129335 $3.913531 10.301515

4a

G = $2562,793815 kcal.mol$1

C 1.558199 0.714028 14.304091

W $0.391703 0.958999 15.129490

C $0.995100 $0.265660 16.762113

C $1.377227 0.265101 18.160534

C $0.161473 0.804752 18.923297

C 2.702064 1.744808 14.416364

C 2.253453 3.124543 13.913721

C 3.232338 1.849102 15.851710

C 3.839812 1.235511 13.508783

Cl $0.792179 $1.108701 13.856942

O $1.744460 1.855739 14.214178

Si $2.242392 2.552767 12.792129

O $1.043248 2.382272 11.675578

Si $0.887810 2.171591 10.036531

O $0.711619 3.645447 9.313796

Si $1.124215 5.226713 9.538248

O $1.306030 5.581778 11.147468

Si $2.478520 5.608186 12.311269

O $2.105064 6.784438 13.383527

Si $2.129086 6.908327 15.070297

O 0.160728 2.177366 16.182946

O $2.530926 4.146701 13.100487

O $3.622136 1.785927 12.326131

Si $5.041277 2.107738 11.523679

O $5.449878 3.691949 11.737959

Si $5.277069 5.169159 11.013330

O $5.124915 4.978842 9.375586

Si $3.931409 4.808241 8.248813

O $4.511331 5.518437 6.884117

O $3.944953 5.930086 11.625960

O $6.591879 6.083176 11.338310

Si $7.917453 6.639029 10.449068

C $1.953261 $0.932584 18.941852

C $2.459368 1.349792 18.051269

O $6.225433 1.153272 12.121206

SI 8

Si $6.374762 0.119533 13.451192

O $4.866608 1.779930 9.912713

Si $3.688560 1.748654 8.748405

O $3.606424 3.206634 7.976233

O 0.443829 1.262598 9.773755

Si 0.828311 0.004518 8.708664

O $2.224086 1.403031 9.436493

O $4.036550 0.586342 7.652193

Si $5.289445 $0.530138 7.450821

O $2.541109 5.557993 8.746258

O 0.109505 6.117407 8.915483

H $2.011786 8.359987 15.381928

H $0.974257 6.162200 15.646310

H $3.409442 6.365962 15.610201

H $7.814038 $0.256632 13.522366

H $5.966734 0.826166 14.700311

H $5.352739 $1.449781 8.623125

H $6.590786 0.180566 7.289267

H 0.139043 7.029883 9.218009

H $4.965017 $1.294597 6.214303

H 2.298790 $0.199786 8.826182

H 0.472791 0.391408 7.312167

H 0.098916 $1.234944 9.097916

H $3.937687 5.452083 6.115020

H $8.586143 5.502430 9.751838

H $7.473602 7.657998 9.455214

H $8.847855 7.254811 11.436069

H $5.531751 $1.093027 13.250267

H 1.356174 0.497683 13.245131

H 1.871087 $0.254076 14.735647

H 4.180072 0.240346 13.817086

H 3.518272 1.174243 12.463265

H 4.700278 1.912978 13.556409

H 1.842622 3.062195 12.899633

H 3.102966 3.816186 13.885341

H 1.493629 3.559495 14.569428

H 4.082315 2.539660 15.893098

H 2.466672 2.217476 16.538219

H 3.582134 0.874296 16.212903

H $3.328586 0.987050 17.489850

H $2.077946 2.246684 17.553948

H $2.808473 1.645078 19.046988

H 0.281345 1.666961 18.420150

H $0.455951 1.116004 19.931949

H 0.610321 0.032783 19.028615

H $2.845173 $1.338410 18.451242

H $2.236822 $0.628290 19.955944

H $1.219054 $1.741494 19.028512

H $0.139291 $0.963792 16.831293

H $1.820081 $0.864557 16.355101

4b

G = $2562,781646 kcal.mol$1

W $0.838045 0.756263 15.266065

O $0.083007 1.327808 16.661120

C 0.899764 0.563015 13.961302

O $1.420124 2.087304 14.068213

Si $2.079308 2.734888 12.689781

O $1.012137 2.498861 11.454642

H 1.341618 $0.432015 14.015256

H 0.489872 0.662629 12.945764

C 1.612310 3.047595 14.160000

H 1.002758 3.265438 15.042711

H 2.483146 3.712348 14.193802

H 1.032846 3.304092 13.267962

H 2.443377 1.622399 11.966580

C 2.979891 1.392504 12.893318

H 3.344536 0.361201 12.826618

C 2.884251 1.268223 15.386187

H 3.748263 1.938563 15.460897

H 3.264057 0.239822 15.362504

C 2.071660 1.583739 14.123937

H 3.853255 2.053207 12.952602

Si $1.918488 7.335120 14.759120

O $1.800204 6.981326 13.109051

O $1.292959 5.693868 10.846600

O $0.916897 3.699684 9.020343

Si $2.323962 5.778886 12.134820

H $1.713359 8.804503 14.889598

H $0.856572 6.598102 15.501432

H $3.264770 6.952166 15.274812

H 2.274396 2.000302 7.965780

H 1.709990 $0.367009 8.198767

Si $1.029807 2.254320 9.815500

O $2.426537 1.482106 9.387154

H 0.292924 1.102814 6.851555

O $3.503425 1.969298 12.382617

Si $5.001968 2.288755 11.743821

O $4.998965 1.909416 10.135307

Si $5.252441 5.339208 11.175306

O $3.941587 3.259913 8.030268

Si $3.954361 1.826478 8.852270

O $5.357033 3.889473 11.965325

O $3.857692 6.108823 11.616326

O $2.781503 5.621328 8.599803

Si $1.290156 5.293140 9.239471

O $0.119609 6.140010 8.454872

H $0.077800 7.074588 8.678230

H $7.248320 8.020931 9.813083

H $4.503350 5.391239 6.137200

O $4.952262 5.543408 6.974063

H $8.603919 7.716866 11.824782

Si $4.224878 4.871331 8.286229

O $5.276456 5.094604 9.537974

O $6.526692 6.266267 11.608235

Si $7.791144 7.027768 10.783968

H $8.621069 6.015356 10.069629

O $4.439830 0.643583 7.832667

Si $5.584637 $0.597893 7.918479

H $5.386626 $1.426115 6.696326

H $6.960493 $0.022923 7.932625

H $5.362576 $1.421473 9.141778

O $6.124764 1.356779 12.473944

H $6.328660 2.258905 14.922641

Si $7.053435 1.472111 13.885032

H $8.349140 2.133045 13.554084

H $7.294193 0.079695 14.353169

Cl $3.055797 0.221057 15.855164

C $0.512320 $1.395874 15.457895

C $0.905197 $2.529480 14.471238

C $2.407529 $2.547237 14.158237

O $2.311493 4.342067 12.967091

O 0.259737 1.315579 9.457641

Si 1.163291 1.011366 8.059942

C $0.540301 $3.860435 15.158678

C $0.136529 $2.452576 13.144654

H 2.287069 1.390245 16.293991

H 0.947923 $2.483594 13.296952

H $0.374486 $1.543182 12.584025

H $0.402424 $3.307098 12.511845

H $2.723474 $1.655034 13.607943

H $2.646992 $3.419445 13.538755

H $3.010677 $2.604429 15.069167

H 0.529787 $3.908085 15.390239

H $0.781058 $4.710402 14.509325

H $1.093679 $3.987435 16.095653

H $1.028632 $1.592907 16.411033

H 0.558301 $1.491810 15.681581

6

G = $1541,870105 kcal.mol$1

SI 9

C 0.340937 2.135930 17.502905

C 1.703823 2.767196 17.872885

C 2.105590 2.441857 19.317434

W $0.009982 0.026318 17.537392

C 1.644470 $1.326872 17.513631

C 1.530162 $2.812051 17.932503

C 1.069266 $2.960919 19.388555

O $0.023925 0.030425 19.262497

O $0.006415 0.028341 15.566853

W $0.003313 0.022014 13.587096

C $1.391906 $1.585783 13.726099

C $1.709457 $2.618012 12.623320

C $0.429465 $3.346795 12.190282

C $2.009619 $0.727334 17.489776

C $3.241682 0.108678 17.908880

C $3.160080 0.548374 19.376481

O $0.010065 0.037780 11.861949

C 2.078150 $0.403989 13.716972

C 3.133450 $0.166735 12.615293

C 3.148059 1.311991 12.203339

C $0.699879 2.029929 13.735679

C $1.410639 2.833230 12.626278

C $2.668659 2.091145 12.152815

C 2.800455 2.294454 16.907534

C 1.557374 4.294602 17.734652

C 2.887762 $1.045793 11.383664

C 4.507173 $0.529885 13.212208

C $3.393101 1.339355 17.002791

C $4.484978 $0.783573 17.730851

C 0.567324 $3.563220 17.001199

C 2.930419 $3.439183 17.793717

C $0.485704 3.103033 11.433772

C $1.832667 4.183801 13.237076

C $2.375840 $1.969028 11.404877

C $2.684108 $3.647174 13.228505

H 2.501195 4.797029 17.977683

H 1.278824 4.577931 16.713323

H 0.788220 4.680032 18.413044

H 3.035810 2.960020 19.578187

H 1.331102 2.759420 20.023354

H 2.257397 1.369928 19.469055

H 3.750464 2.796145 17.124450

H 2.974842 1.215761 16.987005

H 2.535197 2.517609 15.867835

H $4.075684 1.077787 19.664969

H $3.045492 $0.315123 20.040254

H $2.308557 1.208484 19.559954

H $5.395430 $0.238640 18.007163

H $4.594141 $1.114333 16.691721

H $4.423923 $1.676208 18.363262

H $4.306337 1.892939 17.249598

H $2.552090 2.032860 17.113070

H $3.454864 1.048674 15.947754

H $1.001646 3.710403 10.681133

H 0.407354 3.656607 11.748269

H $0.167295 2.170963 10.961223

H $3.223043 2.694991 11.425248

H $2.408215 1.143425 11.673346

H $3.345272 1.882609 12.990850

H $2.949512 $4.410181 12.487366

H $2.241005 $4.158255 14.090987

H $3.612125 $3.167536 13.560498

H $2.630420 $2.732007 10.660169

H $3.306019 $1.462814 11.689610

H $1.714113 $1.238351 10.933969

H $0.662128 $4.144277 11.475340

H 0.271390 $2.659530 11.707991

H 0.072401 $3.810583 13.048533

H 3.678372 $0.888052 10.640987

H 2.895653 $2.109015 11.652454

H 1.928177 $0.814060 10.915547

H 3.956456 1.506578 11.489229

H 2.205458 1.595475 11.726603

H 3.310249 1.963974 13.070482

H 5.301575 $0.386685 12.470318

H 4.744315 0.095214 14.080865

H 4.536107 $1.577681 13.532852

H $2.339080 4.805003 12.488907

H $2.521596 4.044480 14.078252

H $0.963923 4.743525 13.602355

H 1.068735 $4.018084 19.678756

H 1.737259 $2.423509 20.069812

H 0.063521 $2.562299 19.545321

H 2.907620 $4.500582 18.067644

H 3.300095 $3.366164 16.764702

H 3.653412 $2.939777 18.448047

H 0.530380 $4.627659 17.259728

H $0.454535 $3.174565 17.071987

H 0.886393 $3.485369 15.955465

H 2.359684 $0.824161 18.183547

H 2.047259 $1.274773 16.494355

H 0.060004 2.456084 16.491767

H $0.422474 2.512452 18.200527

H $2.156060 $1.087900 16.464411

H $1.938611 $1.606772 18.148910

H $2.312660 $1.030580 13.993336

H $1.090454 $2.116517 14.640028

H $1.327210 2.031216 14.638038

H 0.238401 2.542288 14.025764

H 2.406633 0.092340 14.640289

H 2.028573 $1.484315 13.960125

TS_hydro_oxo

G = 2760,242076 kcal.mol$1

C 0.214325 $1.303680 9.252697

W $0.192975 $0.979128 11.340906

C 0.018090 $2.625309 12.630954

C 0.173261 $4.152455 12.420071

C 1.253011 $4.465973 11.377531

C $0.756769 $1.827554 8.166403

C $1.524583 $3.082839 8.595182

C $1.751051 $0.768164 7.677592

C 0.158302 $2.202326 6.977330

O $1.999144 $1.093121 11.116879

O $1.089423 0.885171 10.184200

Si $0.722400 2.308790 9.546975

O $2.078156 3.032178 8.887501

Si $2.769442 4.509926 8.669448

O $2.401259 5.103231 7.166563

Si $1.207450 5.015310 6.029952

O $1.870424 5.115567 4.535276

Si $2.110771 6.369206 3.430625

Cl 2.089814 $0.368463 11.288569

C $0.271105 0.614383 12.788025

C $1.513795 0.976549 13.639890

C $0.971275 1.926347 14.733330

O 0.421339 2.185600 8.330165

Si 0.865888 2.864836 6.904675

O $0.422117 3.565301 6.131534

O $0.101638 3.362382 10.687920

Si 0.986244 4.569116 10.918917

O 1.619672 4.393251 12.423257

Si 3.051508 4.909259 13.153167

O 2.046405 4.004722 7.145028

Si 2.559005 5.076177 8.298649

O 1.838886 6.547263 8.080625

Si 0.461458 7.210603 7.443962

O $0.140062 6.265691 6.232081

O 1.465946 1.678991 5.937423

Si 1.566897 1.511090 4.260308

O 4.180229 5.275876 8.166567

SI 10

Si 5.406290 4.482815 7.321708

O 2.220133 4.505566 9.812593

O 0.233719 6.040471 10.813453

Si $1.089748 6.708779 10.093882

O $1.650985 7.858002 11.131103

O $0.654033 7.402107 8.651485

O $2.279197 5.589542 9.823446

O 0.797921 8.660162 6.740848

O $4.402221 4.385613 8.794870

Si $5.498946 3.127830 8.555317

C $2.586933 1.728396 12.846579

C $2.141861 $0.239800 14.333940

C $1.170665 $4.763363 12.003682

C 0.596716 $4.769835 13.765884

H $5.213103 2.413076 7.276689

H $5.434830 2.165357 9.693987

H $6.851066 3.752131 8.498535

H 5.412260 3.027348 7.650222

H 6.685731 5.109757 7.758102

H 5.223500 4.668062 5.852523

H 0.252707 1.069194 3.710742

H 2.600957 0.468799 4.003148

H 1.972919 2.799109 3.624996

H $3.103962 5.867519 2.439004

H $2.642931 7.581189 4.118886

H 4.149165 3.946226 12.849609

H 2.794276 4.937879 14.621078

H 3.426193 6.272190 12.674371

H $2.561291 8.123370 10.970027

H 1.227546 9.296982 7.319531

H $0.827536 6.696300 2.744577

H 0.165386 1.518646 12.363037

H 0.480014 0.171021 13.468433

H $0.222963 1.428865 15.360982

H $0.508507 2.815355 14.293645

H $1.789419 2.254532 15.385167

H $2.167099 2.601663 12.341498

H $3.372947 2.074208 13.528069

H $3.061482 1.093845 12.095148

H $2.928448 0.087143 15.023097

H $2.602393 $0.925749 13.616027

H $1.400377 $0.790446 14.925621

H 2.203542 $3.982466 11.629293

H 0.959365 $4.133439 10.377338

H 1.431158 $5.545684 11.322625

H $1.542223 $4.332062 11.071555

H $1.072334 $5.845230 11.859558

H $1.931605 $4.598850 12.774994

H 1.571265 $4.388031 14.091036

H 0.675871 $5.859881 13.683218

H $0.133244 $4.546121 14.551850

H $0.827801 $2.454688 13.320686

H 0.903999 $2.267622 13.190832

H $2.302356 $1.158664 6.814225

H $2.481804 $0.500442 8.443121

H $1.238682 0.145325 7.367702

H 0.710206 $1.329406 6.614707

H $0.444626 $2.593481 6.149379

H 0.884698 $2.974634 7.254851

H $2.126901 $3.457268 7.759859

H $0.843987 $3.889257 8.890696

H $2.204437 $2.874862 9.425655

H 0.781507 $0.457684 8.861140

H 0.940100 $2.114393 9.478325

H $2.109180 $0.201086 10.597789

TSHCl (M06)

G = $2759,712812 kcal.mol$1

C 0.090956 $0.942940 13.095071

C $0.150092 $1.677189 14.418854

C $0.685867 $3.089577 14.196182

W 1.399029 $1.587004 11.569873

C 0.203776 $2.587301 10.110619

C $0.730816 $1.940785 9.073013

C $1.496786 $3.076118 8.383291

C 3.452804 $1.197091 11.097395

C 4.169358 $2.091844 10.064921

C 4.195858 $3.565331 10.464869

O 1.087794 0.582964 10.896736

Si 1.026402 1.821109 9.789671

O $0.433359 1.779846 9.059306

Si $1.584941 2.794432 8.456738

O $1.334702 3.001416 6.852067

Si $0.107980 2.984958 5.757899

O $0.671719 2.494411 4.315678

Si $0.766798 3.283306 2.830877

O 1.804712 $3.035652 12.312030

C 5.617379 $1.587320 10.005154

C 3.546621 $1.934326 8.679653

C 1.135770 $1.709386 15.242626

C $1.208529 $0.870821 15.181605

O 2.225089 1.631353 8.682282

Si 2.488887 1.980686 7.087786

O 3.500659 0.859785 6.472576

Si 5.175233 0.800018 6.666001

O 1.220373 3.201904 10.638139

Si 1.851470 4.718753 10.463951

O 3.045822 4.680424 9.333668

Si 3.292882 4.914762 7.728315

O 4.767223 5.558061 7.480546

Si 6.284012 4.951878 7.886502

O 3.217772 3.452797 6.965112

O 1.073097 1.956035 6.265646

O 2.181302 5.944591 7.100767

Si 0.682902 5.912621 6.417461

O 0.517135 4.498684 5.587253

O 0.514157 7.194653 5.417894

O $0.495009 6.028109 7.547998

Si $0.778138 5.692147 9.135375

O $1.829913 6.763993 9.776550

C $1.751236 $1.029955 9.755010

C 0.062428 $1.193533 8.003325

O 0.655909 5.723033 9.940106

O 2.450502 5.233681 11.872210

Si 2.317733 4.778846 13.498355

O $1.498054 4.221710 9.268835

O $3.047592 2.124990 8.699742

Si $3.902481 1.974636 10.145964

Cl 2.616214 1.071357 13.165742

H 2.224814 6.050313 14.261667

H $4.735331 3.182855 10.351045

H $2.932535 1.817093 11.265248

H $4.751241 0.766027 10.018797

H 5.814652 1.762576 5.733173

H 5.602635 $0.586077 6.366220

H 6.106654 3.642765 8.573012

H 7.063894 4.777221 6.636662

H $1.546772 7.680314 9.792045

H 6.955383 5.923779 8.780317

H 1.081088 3.982890 13.682120

H 3.531256 4.030654 13.885605

H 1.302224 7.450552 4.934434

H 0.601561 3.602266 2.349323

H $1.555820 4.531895 2.975816

H $1.437342 2.344457 1.902366

H 5.500497 1.166512 8.072814

H $0.799498 $1.057925 12.428147

H 0.229689 0.127123 13.280037

H $0.853895 0.146427 15.390112

H $2.143938 $0.797500 14.610153

H $1.438606 $1.353558 16.140643

SI 11

H $1.617793 $3.068892 13.610901

H $0.913255 $3.563601 15.159745

H 0.037029 $3.727046 13.675872

H 0.938699 $2.139294 16.233670

H 1.906380 $2.319184 14.756279

H 1.541968 $0.698608 15.374173

H 3.445324 $0.875048 8.401372

H 2.545286 $2.379318 8.626563

H 4.158752 $2.433556 7.916412

H 3.201070 $4.025235 10.451085

H 4.833904 $4.129817 9.772076

H 4.599456 $3.692856 11.477745

H 5.656499 $0.523986 9.734622

H 6.189062 $2.151353 9.254648

H 6.117712 $1.706249 10.974416

H 3.961837 $1.260868 12.071346

H 3.533696 $0.149211 10.777047

H $0.611912 $0.652043 7.327593

H 0.761021 $0.463068 8.426633

H 0.654957 $1.892983 7.398397

H $0.809318 $3.782796 7.900540

H $2.163539 $2.673722 7.609091

H $2.111603 $3.635936 9.099844

H $2.447609 $0.612375 9.014177

H $2.343205 $1.596868 10.489717

H $1.279904 $0.183208 10.266913

H 0.897383 $3.283582 9.606870

H $0.400352 $3.234527 10.774820

H 1.635258 0.945569 11.756790

TSCMe4

G = $2759,702359 kcal.mol$1

C 1.297262 0.244920 13.302729

W 1.823695 $1.167476 11.861533

O 0.681088 $2.383958 12.149705

C 0.035795 0.228962 14.175726

C 0.109608 1.474293 15.067351

C $1.229599 0.305893 13.323722

C $0.002249 $1.017088 15.056934

C 1.593899 $1.739751 9.503999

C 0.416408 $2.223920 8.625736

C $0.147701 $1.064401 7.801704

C 3.312861 $2.240610 12.957304

C 3.959394 $3.554085 12.447562

C 4.849902 $3.288984 11.235950

Cl 3.684494 0.106723 10.963032

O 0.430235 0.241946 10.744095

Si 0.450782 1.691260 10.030689

O 1.568007 1.722613 8.821162

Si 1.786402 2.340351 7.323454

O 2.606771 3.758994 7.448683

Si 2.836282 4.996140 8.517759

O 2.622012 4.486341 10.065550

Si 1.445095 4.374003 11.210988

O 0.311795 5.539765 10.994613

Si $1.110406 5.810818 10.209117

O $1.997622 6.922801 11.013721

C 0.991034 $3.274221 7.671451

C $0.693499 $2.843531 9.467692

C 2.906503 $4.606383 12.102293

C 4.833747 $4.103708 13.578636

O 0.754199 2.881353 11.132415

O $1.032012 1.953325 9.361788

Si $2.128662 3.134687 9.045381

O $3.597364 2.456234 9.248400

Si $3.914468 0.847390 9.648227

O 2.094599 4.566066 12.693098

Si 3.348778 3.737701 13.452058

O $1.925364 4.385068 10.090305

O $1.943676 3.670004 7.501825

Si $0.774602 3.777611 6.352945

O 0.338811 2.583384 6.567690

O $0.840875 6.441505 8.721724

Si 0.285717 6.433754 7.523069

O 1.768022 6.203166 8.199203

O 0.230244 7.837725 6.688959

O $0.031827 5.246947 6.436195

O 2.634680 1.277418 6.422884

Si 2.365065 0.679982 4.873427

O $1.440478 3.629903 4.876409

Si $1.466688 4.682341 3.562010

O 4.360574 5.534177 8.331277

Si 5.575998 5.033958 7.279117

H $5.384623 0.745840 9.802499

H $3.225028 0.492796 10.917516

H $3.445400 $0.050361 8.558393

H 2.040769 1.794119 3.946827

H 1.243789 $0.296205 4.908103

H 5.900932 3.607375 7.526982

H 5.128951 5.216173 5.874689

H $2.256495 6.691441 11.907731

H 6.750073 5.892526 7.562469

H 2.907854 3.444278 14.840060

H 4.553349 4.601905 13.472513

H 3.618984 2.473917 12.714098

H 0.245016 8.639664 7.215068

H $0.078786 4.932513 3.096961

H $2.114329 5.959870 3.948056

H $2.249573 4.000957 2.503986

H 3.618493 0.005796 4.460318

H 1.427595 1.223698 12.818728

H 2.200598 0.077852 13.935712

H 1.004100 1.457949 15.705023

H 0.141841 2.389625 14.459666

H $0.769292 1.530913 15.722983

H $1.232716 1.208034 12.698662

H $2.113352 0.338708 13.974768

H $1.321590 $0.560774 12.658366

H $0.881341 $0.990247 15.713304

H $0.059601 $1.935556 14.460662

H 0.888031 $1.074237 15.699277

H 5.621158 $2.542407 11.463421

H 4.284162 $2.916502 10.372587

H 5.353625 $4.215035 10.928097

H 2.291253 $4.324613 11.236915

H 3.393774 $5.560523 11.861873

H 2.221329 $4.777841 12.942515

H 5.604998 $3.378849 13.868817

H 5.339876 $5.026689 13.264954

H 4.232738 $4.335180 14.467698

H 2.770245 $2.486129 13.890892

H 4.117567 $1.537884 13.219005

H $0.842457 $1.447596 7.042970

H $0.703637 $0.349000 8.419574

H 0.651918 $0.517424 7.282938

H 1.792506 $2.851174 7.051140

H 0.206681 $3.648155 7.000362

H 1.399894 $4.131553 8.223451

H $1.497885 $3.207979 8.815054

H $0.325622 $3.688748 10.063617

H $1.125205 $2.109458 10.161079

H 2.339529 $1.197092 8.907696

H 2.091513 $2.622653 9.936762

H 0.990672 $0.751240 10.072647

SI 1