ESM for Correlation Between Regioselectivity and Site Charge in Propene Polymerisation

ESM for Correlation between regioselectivity and site charge in propene polymerisation

Catalysed by metallocene

Y.Liu, Y.Liu, M.G.B.Drew

Contents

I Charges

1.01 NBO PBEPBE/LANL2DZ

1.02 Mulliken partial charges,PBEPBE/LANL2DZ

1.03 Mulliken partial charges,B3LYP/LANL2DZ

1.04 Partial Charge versus Radius

1.05 Chelp, ChelpG, MK charge

II Structures

1. PBEPBE/LANL2DZ

1.01 1-perp

1.02 1-cis

1.03 1-trans

1.04 ts12

1.05 ts21

1.06 2-γ12

1.07 2-γtoβts12

1.08 2-β12

1.09 2-α12

1.10 2-α12-symm

1.11 2t-γ21

1.12 2-γtoβts21

1.13 2t-β21-1

1.14 2t-β21-2

1.15 2s-β21

1.16 Coefficients of C1, C2, and C4 for 1-cis and 1-trans from HOMO-1 to LUMO+2

2. B3LYP /LANL2DZ

2.01 1-perp

2.02 1-cis

2.3 1-trans

2.04 ts12

2.05 ts21

2.06 2-12

2.07 2-21

2.08 Coefficients of C1, C2, and C4 for 1-cis and 1-trans from HOMO-1 to LUMO+2


I Charges

1.01 PBEPBE/LANL2DZ

NBO / 2-γ12 / 2-b12 / 2-α12 / 2-γ21 / 2t-b21
Zr / 1.344 / 1.443 / 1.463 / 1.290 / 1.430
C1 / -0.782 / -0.763 / -0.739 / -0.485 / -0.406
C2 / -0.237 / -0.179 / -0.200 / -0.517 / -0.508
C3 / -0.646 / -0.651 / -0.661 / -0.674 / -0.672
C4 / -0.698 / -0.651 / -0.660 / -0.678 / -0.645
*H(agostic) / 0.220 / 0.158 / 0.216 / 0.218 / 0.169
*H / 0.302 / 0.249 / 0.242 / 0.305 / 0.268
*C-H(agostic) / 1.135 / 1.206 / 1.155 / 1.138 / 1.190
*C-H / 1.104 / 1.108 / 1.109 / 1.103 / 1.105
Relative Energy / -4.70 / -6.70 / 1.99 / -1.77 / -4.58

1.02


Selected Mulliken partial charges (a.u.) and bond lengths (?) at PBEPBE/LANL2DZ level.

Relative energies in kcal/mol

Mulliken / 1-perp / 1-cis / 1-trans / ts-12 / ts-21
Zr / 0.572 / 0.594 / 0.569 / 0.484 / 0.471
C1 / -0.619 / -0.615 / -0.596 / -0.672 / -0.463
C2 / 0.052 / 0.078 / 0.065 / -0.018 / -0.212
C3 / -0.760 / -0.749 / -0.754 / -0.746 / -0.755
C4 / -0.967 / -0.981 / -0.969 / -0.890 / -0.855
*H(agostic) / n/a / n/a / n/a / 0.242 / 0.239
*H(other) / 0.282 / 0.251 / 0.272 / 0.306 / 0.305
*C-H(agostic) / n/a / n/a / n/a / 1.149 / 1.152
*C-H(other) / 1.109 / 1.108 / 1.107 / 1.100 / 1.099
Relative Energy / 0.00 / 0.24 / 0.26 / 7.13 / 11.72
Mulliken / 2-γ12 / 2-b12 / 2-α12 / 2-α12-symm / 2-γ21 / 2-b21
Zr / 0.479 / 0.548 / 0.701 / 0.718 / 0.490 / 0.571
C1 / -0.692 / -0.665 / -0.586 / -0.600 / -0.473 / -0.341
C2 / -0.092 / 0.0535 / -0.096 / -0.086 / -0.327 / -0.279
C3 / -0.692 / -0.701 / -0.676 / -0.693 / -0.767 / -0.750
C4 / -0.774 / -0.701 / -0.681 / -0.675 / -0.732 / -0.698
*H(agostic) / 0.282 / 0.108 / 0.174 / 0.199 / 0.266 / 0.157
*H / 0.322 / 0.240 / 0.247 / 0.226 / 0.326 / 0.289
Relative Energy / -4.70 / -6.70 / 1.99 / 5.06 / -1.77 / -4.57


1.03 Selected Mulliken partial charges (a.u.) and bond lengths (Ǻ) at B3LYP/LANL2DZ level.

Relative Energies in kcal/mol

Mulliken / 1-perp / 1-cis / 1-trans / ts-12 / ts-21
Zr / 0.634 / 0.653 / 0.644 / 0.544 / 0.534
C1 / -0.610 / -0.598 / -0.591 / -0.665 / -0.407
C2 / 0.077 / 0.081 / 0.076 / 0.027 / -0.228
C3 / -0.705 / -0.693 / -0.698 / -0.694 / -0.696
C4 / -0.940 / -0.942 / -0.944 / -0.853 / -0.817
*H(agostic) / n/a / n/a / n/a / 0.223 / 0.223
*H / 0.290 / 0.250 / 0.229 / 0.253 / 0.292
*C-H(agostic) / n/a / n/a / n/a / 1.134 / 1.137
*C-H / 1.090 / 1.102 / 1.101 / 1.091 / 1.091
Relative Energy / 0.00 / -0.66 / -0.18 / 12.04 / 17.17

1.04 Charges as a function of radius of Zr

PBEPBE

TS12-Chelp

TS12-ChelpG

TS12-MK

1-  perp-chelp

1-  perp-ChelpG

1-perp-MK


1.05

PBEPBE

1-per-chelp / mulliken
R / Zr / C1 / C2 / C3 / C4
0.73 / 2.242444 / -1.13732 / 0.199853 / -0.61216 / -2.121703
0.8 / 2.078669 / -0.86728 / 0.104941 / -0.57626 / -1.808957
0.86 / 2.078669 / -0.86728 / 0.104941 / -0.57626 / -1.808957
0.98 / 2.021757 / -0.80942 / 0.079548 / -0.54334 / -1.716109
1.09 / 1.81418 / -0.46902 / 0.014043 / -0.52688 / -1.651603
1.26 / 1.624479 / -0.34717 / -0.05902 / -0.41934 / -1.466132
1.48 / 1.366349 / -0.4388 / 0.003765 / -0.3484 / -1.083347
1.55 / 1.219057 / -0.42719 / -0.01094 / -0.29369 / -0.842689
1.75 / 0.919823 / -0.24849 / -0.07741 / -0.18154 / -0.486471
2.06 / 0.855252 / -0.19366 / -0.08363 / -0.17058 / -0.467286
ts12-chelp
0.73 / 2.363339 / -1.89001 / 0.923113 / -0.22338 / -1.604504
0.8 / 2.214499 / -1.6765 / 0.825806 / -0.21461 / -1.442147
0.86 / 2.154474 / -1.56168 / 0.767498 / -0.197 / -1.37182
0.98 / 1.98216 / -1.35766 / 0.693853 / -0.2263 / -1.199864
1.09 / 1.845808 / -1.19389 / 0.646742 / -0.25471 / -1.08796
1.26 / 1.720165 / -1.05498 / 0.595542 / -0.27452 / -0.960973
1.48 / 1.415576 / -0.83304 / 0.392345 / -0.13088 / -0.697955
1.55 / 1.250788 / -0.66311 / 0.479567 / -0.24548 / -0.820672
1.75 / 0.945809 / -0.53341 / 0.524977 / -0.33974 / -0.633337
2.06 / 0.774234 / -0.43965 / 0.449561 / -0.2994 / -0.512315
1-per-MK
0.73 / 1.282021 / -0.27448 / 0.095639 / -0.38682 / -1.357983
0.8 / 1.282021 / -0.27448 / 0.095639 / -0.38682 / -1.357983
0.86 / 1.282021 / -0.27448 / 0.095639 / -0.38682 / -1.357983
0.98 / 1.282021 / -0.27448 / 0.095639 / -0.38682 / -1.357983
1.09 / 0.546994 / -0.54838 / 0.224833 / -0.42801 / -0.736531
1.26 / 0.546994 / -0.54838 / 0.224833 / -0.42801 / -0.736531
1.48 / 0.626306 / -0.48994 / 0.18886 / -0.41964 / -0.796653
1.55 / 0.601666 / -0.50779 / 0.199586 / -0.42172 / -0.777329
1.75 / 0.537317 / -0.54569 / 0.224656 / -0.43074 / -0.820941
2.06 / 0.500663 / -0.56444 / 0.236605 / -0.43768 / -0.808323
2.26 / 0.52441 / -0.55577 / 0.231251 / -0.43416 / -0.825154
1-per-ChelpG
0.73 / 2.825247 / -2.18202 / 0.854189 / -0.76152 / -3.501552
0.8 / 2.526158 / -1.69095 / 0.614268 / -0.69417 / -2.852457
0.86 / 2.317285 / -1.346 / 0.430314 / -0.62336 / -2.412861
0.98 / 1.964192 / -0.87306 / 0.191228 / -0.52953 / -1.749208
1.09 / 1.580429 / -0.41855 / 0.016438 / -0.46562 / -1.143049
1.26 / 1.240299 / -0.17964 / -0.03248 / -0.43351 / -0.831891
1.48 / 0.891375 / -0.18574 / 0.063857 / -0.41615 / -0.497101
1.55 / 0.8346 / -0.17097 / 0.058533 / -0.40186 / -0.46356
1.75 / 0.682117 / -0.30797 / 0.148838 / -0.36163 / -0.510197
2.06 / 0.538935 / -0.40495 / 0.191784 / -0.30557 / -0.501889
2.26 / 0.506351 / -0.46277 / 0.213008 / -0.29048 / -0.557335
TS12-MK
0.73 / 0.500648 / -0.64882 / 0.308507 / -0.58164 / -0.570825
0.8 / 0.500648 / -0.64882 / 0.308507 / -0.58164 / -0.570825
0.86 / 0.500648 / -0.64882 / 0.308507 / -0.58164 / -0.570825
0.98 / 0.500648 / -0.64882 / 0.308507 / -0.58164 / -0.570825
1.09 / 0.500648 / -0.64882 / 0.308507 / -0.58164 / -0.570825
1.26 / 0.500648 / -0.64882 / 0.308507 / -0.58164 / -0.570825
1.48 / 0.420562 / -0.60874 / 0.273993 / -0.57799 / -0.601355
1.55 / 0.420562 / -0.60874 / 0.273993 / -0.57799 / -0.601355
1.75 / 0.352043 / -0.61075 / 0.268264 / -0.58184 / -0.630417
2.06 / 0.335339 / -0.64472 / 0.289041 / -0.58805 / -0.642096
2.26 / 0.380731 / -0.67484 / 0.310877 / -0.5877 / -0.628894
TS12-ChelpG
0.73 / 2.907529 / -3.3619 / 1.953787 / -0.72311 / -2.537554
0.8 / 2.679422 / -3.00074 / 1.802452 / -0.78417 / -2.325286
0.86 / 2.383857 / -2.60258 / 1.581479 / -0.7996 / -1.895902
0.98 / 2.003768 / -1.96151 / 1.178537 / -0.74596 / -1.370575
1.09 / 1.68365 / -1.56247 / 0.93489 / -0.66138 / -1.124318
1.26 / 1.183953 / -0.92821 / 0.59362 / -0.61655 / -0.599558
1.48 / 0.882633 / -0.68118 / 0.451599 / -0.52891 / -0.433164
1.55 / 0.760385 / -0.60653 / 0.410958 / -0.51391 / -0.395648
1.75 / 0.607639 / -0.5661 / 0.378404 / -0.45513 / -0.373506
2.06 / 0.455353 / -0.57391 / 0.364766 / -0.41422 / -0.39004
2.26 / 0.410056 / -0.55844 / 0.337063 / -0.4085 / -0.422298
B3LPY
TS12

B3LPY

TS12 / chelp / mulliken
Zr / C1 / C2 / C3 / C4 / H(agostic) / H / Zr / C1 / C2 / C3 / C4 / H(agostic) / H
0.73 / 2.9461 / -3.39153 / 2.041914 / -0.72111 / -2.49358 / 0.019216 / 0.783329
0.8 / 2.692476 / -3.08214 / 1.898522 / -0.7801 / -2.16681 / 0.01476 / 0.680011
0.86 / 2.438802 / -2.63655 / 1.654486 / -0.78013 / -1.84062 / -0.000268 / 0.581845
0.98 / 2.115542 / -2.12127 / 1.323141 / -0.72964 / -1.46367 / -0.005084 / 0.468431
1.09 / 1.736286 / -1.61857 / 1.02325 / -0.65275 / -1.09135 / 0.006039 / 0.352284
1.26 / 1.292036 / -1.00038 / 0.664285 / -0.58278 / -0.66472 / 0.007846 / 0.224512
1.48 / 0.973378 / -0.72493 / 0.52351 / -0.52866 / -0.44594 / 0.025035 / 0.155789
1.55 / 0.865799 / -0.62599 / 0.466297 / -0.50988 / -0.43378 / 0.046154 / 0.152324
1.75 / 0.716449 / -0.59917 / 0.442474 / -0.45572 / -0.40185 / 0.071438 / 0.139857
2.06 / 0.556574 / -0.57594 / 0.40772 / -0.40765 / -0.39676 / 0.10178 / 0.13796
2.26 / 0.517667 / -0.56652 / 0.377422 / -0.40193 / -0.4425 / 0.119978 / 0.152293 / 0.533985 / -0.66384 / 0.02811 / -0.6928 / -0.8547 / 0.2231 / 0.292373


1.05

ChelpG-PBEPBE / 1-perp / 1-cis / 1-trans / ts-12 / ts-21
Zr / 0.553636 / 0.553050 / 0.489501 / 0.468639 / 0.397650
C1 / -0.400620 / -0.396467 / -0.332079 / -0.558773 / -0.103541
C2 / 0.189966 / 0.188872 / 0.107573 / 0.360415 / -0.032830
C3 / -0.308916 / -0.276988 / -0.285498 / -0.423106 / -0.339486
C4 / -0.508391 / -0.428216 / -0.399867 / -0.386555 / -0.323499
*H(agostic) / 0.102413 / 0.094612
*H(other) / 0.145736 / 0.132334
Relative Energy / 0.00 / 0.24 / 0.26 / 7.13 / 11.72
MK-PBEPBE / 1-perp / 1-cis / 1-trans / ts-12 / ts-21
Zr / 0.517935 / 0.475371 / 0.412138 / 0.355592 / 0.250928
C1 / -0.553882 / -0.530392 / -0.500229 / -0.649739 / -0.319393
C2 / 0.231904 / 0.230066 / 0.165084 / 0.293701 / 0.082973
C3 / -0.426574 / -0.425379 / -0.448904 / -0.587710 / -0.529624
C4 / -0.820673 / -0.774625 / -0.770132 / -0.644768 / -0.510587
*H(agostic) / 0.194586 / 0.168793
*H(other) / 0.219914 / 0.191963
Relative Energy / 0.00 / 0.24 / 0.26 / 7.13 / 11.72

B3LPY

B3LPY-MK / 1-perp / 1-cis / 1-trans / ts-12 / ts-21
Zr / 0.593551 / 0.624945 / 0.583940 / 0.487090 / 0.376651
C1 / -0.571834 / -0.527147 / -0.501812 / -0.667297 / -0.268692
C2 / 0.245966 / 0.270096 / 0.166048 / 0.326890 / 0.037329
C3 / -0.388229 / -0.461551 / -0.423551 / -0.560371 / -0.484356
C4 / -0.773384 / -0.762192 / -0.684245 / -0.627316 / -0.509903
*H(agostic) / 0.178055 / 0.162386
*H(other) / 0.206032 / 0.185340
Relative Energy / 0.00 / -0.66 / -0.18 / 12.04 / 17.17
B3LPY-ChelpG / 1-perp / 1-cis / 1-trans / ts-12 / ts-21
Zr / 0.622513 / 0.629005 / 0.589481 / 0.573042 / 0.509558
C1 / -0.421317 / -0.394720 / -0.370410 / -0.569151 / -0.059640
C2 / 0.200155 / 0.198838 / 0.134685 / 0.398972 / -0.083356
C3 / -0.246474 / -0.261915 / -0.266505 / -0.407628 / -0.281152
C4 / -0.463234 / -0.408209 / -0.393029 / -0.383071 / -0.307495
*H(agostic) / 0.094491 / 0.085416
*H(other) / 0.134451 / 0.123021
Relative Energy / 0.00 / -0.66 / -0.18 / 12.04 / 17.17


II Structure

1 PBEPBE/LANL2DZ

1.01 1-perp HF=-590.5183513

Standard orientation:

------

Center Atomic Atomic Coordinates (Angstroms)

Number Number Type X Y Z

------

1 6 0 1.729388 -1.694167 -1.059545

2 6 0 0.292117 -0.103389 2.397465

3 6 0 2.181256 -1.670014 0.307801

4 6 0 -1.226956 -2.179361 0.043785

5 40 0 0.207099 0.005071 0.151619

6 6 0 -2.442975 -1.592024 0.321717

7 6 0 1.956531 -0.393976 -1.629069

8 6 0 2.704175 -0.360633 0.583814

9 6 0 2.565229 0.432320 -0.611434

10 6 0 -0.286473 2.010639 -1.335236

11 6 0 -1.559161 1.404956 -1.088035

12 1 0 -2.665730 -1.333453 1.369197

13 6 0 0.217018 2.515782 -0.074529

14 1 0 -0.735619 0.018774 2.799618

15 6 0 -1.853796 1.539078 0.323172

16 1 0 0.923059 0.664862 2.885433

17 1 0 0.692890 -1.091037 2.703299

18 1 0 -1.024250 -2.584668 -0.955738

19 1 0 -0.703608 2.538148 1.986505

20 1 0 -0.582370 -2.531839 0.862126

21 6 0 -0.766079 2.242791 0.940706

22 1 0 -2.203208 0.949561 -1.841741

23 1 0 1.135021 3.085805 0.065472

24 1 0 -2.773141 1.234227 0.822481

25 1 0 0.199537 2.110322 -2.305253

26 1 0 1.339260 -2.563423 -1.589520

27 1 0 1.770610 -0.105040 -2.663389

28 1 0 2.929069 1.449376 -0.749580

29 1 0 2.164823 -2.508626 1.004758

30 1 0 3.151825 -0.034654 1.521907

31 6 0 -3.556293 -1.390368 -0.665257

32 1 0 -4.374625 -2.093663 -0.408078

33 1 0 -4.001276 -0.381168 -0.600522

34 1 0 -3.250096 -1.596152 -1.703880

1.02 1-cis HF=-590.5179607

Standard orientation:

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Center Atomic Atomic Coordinates (Angstroms)

Number Number Type X Y Z

------

1 6 0 0.020491 2.582501 0.174486

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