Supporting information
Ligand structures of optimized zirconocene dichlorides.
1 2 3 4 5 6
Si
Si
O
Si Si
7 8 9 10 11 12 13 14 15 16
Si
O Si
Si Si
17 18 19 20 21 22 23 24 25 26
Si
Si N
N
Si
27 28 29 30 31 32 33 34 35 36 37
Si Si Si Si
38 39 40 41 42 43 44 45 46 47
Si
Si
48 49 50 51 52 53 54 55 56 57
58 59 60 61 62
O Si O Si O Si O Si O Si
O Si O Si
O
Si Si O
O Si O Si
° ° °
HF Exp. HF Exp. HF Exp. HF Exp. HF Exp.
1 2.491 2.415 2.257 2.239 97.9 98.7 125.8 126.5 64.2 63.7 1
2 2.481 2.414 2.271 2.242 96.9 94.3 125.8 125.7 60.5 57.8 2
3 2.500 2.431 2.255 2.229 96.7 96.3 124.9 125.1 59.8 57.7 2
4 2.481 2.411 2.270 2.254 99.0 99.3 126.6 125.9 60.0 61.0 3
5 2.501 2.438 2.247 2.229 96.8 98.1 124.7 125.2 58.3 58.3 4
6 2.487 2.432 2.267 2.246 98.8 97.9 126.8 126.3 60.3 59.5 5
7 2.484 2.435 2.257 2.197 101.6 98.0 123.7 125.4 61.7 60.1 6
8 2.483 2.434 2.246 2.210 101.6 102.5 116.7 118.3 73.2 71.5 7
9 2.497 2.436 2.237 2.208 100.1 97.2 123.9 123.9 61.3 59.7 8
10 2.470 2.431 2.281 2.241 98.8 98.8 125.6 127.8 63.3 61.8 9
11 2.495 2.436 2.264 2.233 97.1 94.8 130.3 128.8 51.4 53.5 9
12 2.493 2.433 2.255 2.221 100.4 99.7 120.6 122.5 75.0 72.9 10
13 2.493 2.431 2.272 2.248 99.8 98.9 131.0 130.9 51.3 52.2 11
14 2.498 2.439 2.247 2.215 98.1 96.7 124.4 125.8 61.4 60.3 12
15 2.473 2.420 2.286 2.238 99.8 99.0 127.2 128.0 61.9 60.2 13
16 2.499 2.436 2.250 2.212 97.8 98.6 124.4 125.3 59.4 60.3 14
17 2.498 2.435 2.257 2.201 100.1 98.7 132.1 130.8 49.7 51.1 15
Molecule Zr-Cl (Å) Zr-Cp’(Å) Cl-Zr-Cl (°) Cp’-Zr-Cp’(°) Cp’-Cp’(°) Ref.
HF Exp. HF Exp. HF Exp. HF Exp. HF Exp.
19 2.483 2.428 2.253 2.199 101.7 99.6 119.1 120.6 73.1 69.6 17
20 2.484 2.431 2.261 2.223 97.7 95.9 124.1 123.8 63.0 62.4 18
21 2.472 2.411 2.299 2.242 98.0 98.3 127.9 127.9 65.5 61.9 19
22 2.504 2.449 2.253 2.232 95.3 96.1 125.9 126.1 60.5 60.4 20
23 2.502 2.443 2.259 2.227 96.3 96.8 131.1 130.2 53.5 55.8 21
24 2.487 2.431 2.267 2.231 101.1 97.1 127.3 127.2 59.1 58.9 22
25 2.486 2.444 2.244 2.217 97.8 97.2 123.7 123.8 61.1 59.0 23
26 2.480 2.427 2.265 2.224 100.4 98.6 124.4 125.9 63.5 61.8 23
27 2.478 2.430 2.265 2.213 101.0 97.9 125.0 126.9 62.6 60.4 24
28 2.497 2.428 2.251 2.211 101.9 99.0 124.6 126.3 62.7 61.0 25
29 2.498 2.430 2.268 2.228 100.9 98.0 124.6 126.2 65.1 63.7 25
30 2.504 2.441 2.244 2.211 100.0 98.4 126.5 127.7 58.5 57.7 26
31 2.476 2.432 2.253 2.207 99.2 98.1 117.8 118.5 73.5 71.2 27
32 2.497 2.450 2.245 2.203 98.5 97.0 130.8 129.6 49.7 50.2 28
33 2.484 2.422 2.279 2.237 93.3 95.0 126.9 129.1 61.8 59.2 29
34 2.491 2.428 2.267 2.237 94.0 94.8 126.9 127.2 59.6 57.7 30
35 2.495 2.441 2.253 2.196 99.0 95.7 131.6 131.5 50.9 51.2 31
36 2.493 2.442 2.235 2.177 101.0 98.8 123.5 123.2 58.3 55.3 32
38 2.502 2.448 2.252 2.215 100.1 100.1 124.3 124.8 62.0 61.2 34
39 2.507 2.438 2.284 2.239 92.8 89.6 132.6 130.3 51.0 54.1 35
40 2.472 2.423 2.280 2.247 100.2 99.3 126.4 128.0 61.4 60.8 36
41 2.478 2.420 2.278 2.248 98.8 96.8 127.7 128.6 61.8 59.1 37
42 2.486 2.438 2.234 2.187 101.8 97.9 119.6 119.8 64.8 62.7 38
43 2.498 2.432 2.250 2.221 96.1 96.5 131.5 131.3 51.6 52.9 39
44 2.481 2.439 2.255 2.213 100.0 99.8 124.5 125.1 60.4 60.0 40
45 2.474 2.429 2.247 2.199 102.1 100.1 115.8 117.1 72.9 71.6 41
46 2.469 2.429 2.280 2.254 98.8 98.3 125.5 127.6 63.5 63.3 42
47 2.494 2.434 2.261 2.231 98.5 99.4 124.5 126.5 63.2 61.7 42
48 2.486 2.437 2.246 2.199 101.4 98.3 115.4 116.4 73.7 72.1 43
49 2.482 2.437 2.248 2.191 101.5 98.3 115.1 116.3 73.6 71.5 44
50 2.475 2.424 2.271 2.235 98.0 97.1 124.9 125.3 61.8 60.4 45
51 2.478 2.426 2.270 2.227 99.4 97.6 125.7 126.3 60.3 59.7 45
52 2.487 2.406 2.258 2.207 98.7 97.2 115.0 117.4 75.8 76.2 46
53 2.494 2.441 2.261 2.231 98.7 97.3 124.6 126.4 63.3 61.8 47
54 2.473 2.414 2.261 2.211 99.3 99.1 117.8 118.6 75.3 73.5 48
55 2.481 2.414 2.277 2.236 98.5 97.2 127.6 129.5 58.9 57.8 49
Molecule Zr-Cl (Å) Zr-Cp’(Å) Cl-Zr-Cl (°) Cp’-Zr-Cp’(°) Cp’-Cp’(°) Ref.
HF Exp. HF Exp. HF Exp. HF Exp. HF Exp.
57 2.476 2.420 2.271 2.215 98.3 96.2 117.8 118.5 76.5 73.2 49
58 2.505 2.440 2.270 2.229 99.0 98.6 133.4 132.8 52.0 53.6 50
59 2.502 2.428 2.271 2.233 97.2 97.6 125.0 126.7 64.0 62.6 51
60 2.479 2.432 2.240 2.191 103.4 100.2 114.9 116.6 72.7 71.4 52
61 2.492 2.452 2.238 2.187 101.1 97.5 123.8 125.0 58.4 57.4 53
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