Journal Name: Structural Chemistry
Supplementary Material
The Role of Cesium Fluoride in Aryl Propargyl Ether Claisen Rearrangement and its Mechanistic Elucidation: A Theoretical Study.
MengistuGemech Menkir1,VenkatesanSrinivasadesikan2 and Shyi-LongLee1,
1Department of Chemistry and Biochemistry, National Chung Cheng University,Chia-Yi, Taiwan.
2Department of Chemistry, National Chiao Tung University, Hsinchu, Taiwan.
Corresponding authorE-mail:
TableS1. The relative free energies for all speciesin the reaction in gas and solvent phases at M06/6-31+G(d,p)/LANL2DZ// B3LYP/6-31+G(d)/LANL2DZ level. (Unit: kcalmol-1) The optimized geometry of Ts2a-CsF in gas phase is not found.
M06/6-31+G(d,p)/LANL2DZ// B3LYP/6-31+G(d)/LANL2DZGas / Solvent
1-CsF / 0.0 / 0.0
Ts1-CsF / 39.2 / 37.1
Int1-CsF / 6.4 / -3.4
Ts2a-CsF / --- / -2.1
Int2a + HF / -18.6 / -19.8
Ts3a-CsF / -5.3 / -8.9
Product A + CsF / -50.3 / -49.4
Ts2b-CsF / 51.1 / 50.6
Int2b-CsF / -36.4 / -27.0
Ts3b-CsF / -0.2 / 5.6
Int3b-CsF / -23.0 / -21.9
Ts4b-CsF / -11.8 / -12.2
Int4b-CsF / -8.3 / -16.2
Ts5b-CsF / -7.0 / -4.2
Product B + CsF / -34.7 / -34.1
Cartesian coordinates (Ǻ) for optimizedstructures in N,N-diethylaniline at B3LYP/6-31G(d)/LANL2DZ level with PCM model.The coordinates of the optimized structures in gas phase are not included.
1
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
1 6 0 -2.617767 -0.573337 0.495153
2 6 0 -2.756273 0.762512 0.094996
3 6 0 -1.642468 1.444402 -0.396665
4 6 0 -0.395213 0.813267 -0.495417
5 6 0 -0.271318 -0.523754 -0.099074
6 6 0 -1.385034 -1.215959 0.400245
7 8 0 0.891716 -1.256175 -0.163514
8 6 0 2.065928 -0.662943 -0.726892
9 6 0 2.734259 0.282733 0.175044
10 6 0 3.307753 1.050107 0.914079
11 1 0 -3.474581 -1.119308 0.881771
12 1 0 -3.718138 1.262007 0.169323
13 1 0 -1.731119 2.482933 -0.705498
14 1 0 0.456234 1.374379 -0.863209
15 1 0 -1.265233 -2.251887 0.704225
16 1 0 2.728070 -1.508470 -0.933136
17 1 0 1.828171 -0.184104 -1.685529
18 1 0 3.803660 1.731680 1.571351
CsF
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
1 55 0 0.000000 0.000000 0.404130
2 9 0 0.000000 0.000000 -2.469682
1-CsF
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
1 6 0 4.910943 -1.542987 0.021937
2 6 0 3.970034 -2.386441 0.625918
3 6 0 2.627776 -1.995491 0.658641
4 6 0 2.207173 -0.780391 0.102772
5 6 0 3.162955 0.055701 -0.492033
6 6 0 4.513140 -0.324888 -0.531302
7 8 0 2.868014 1.253238 -1.103478
8 6 0 1.652435 1.943069 -0.743888
9 6 0 1.779102 2.628588 0.548389
10 6 0 1.878011 3.205285 1.609270
11 1 0 5.959620 -1.828807 -0.013495
12 1 0 4.279484 -3.332871 1.061763
13 1 0 1.885753 -2.645674 1.117205
14 1 0 1.150862 -0.511930 0.104007
15 1 0 5.233724 0.342332 -0.996388
16 1 0 1.517280 2.679962 -1.541729
17 1 0 0.776650 1.272021 -0.737032
18 1 0 1.969056 3.701877 2.550701
19 55 0 -3.615306 -0.288206 0.007864
20 9 0 -0.787123 0.148204 -0.438658
Ts1-CsF
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
1 6 0 3.450822 -1.302813 -1.140993
2 6 0 3.477981 -1.735794 0.214230
3 6 0 2.539763 -1.265113 1.105248
4 6 0 1.549186 -0.309026 0.703226
5 6 0 1.470889 0.047884 -0.692849
6 6 0 2.491963 -0.413849 -1.580699
7 8 0 0.545874 0.869846 -1.103197
8 6 0 0.930949 2.689146 -0.463595
9 6 0 1.705247 2.446434 0.642789
10 6 0 2.234536 1.561325 1.363341
11 1 0 4.195995 -1.682159 -1.836618
12 1 0 4.232577 -2.450221 0.533068
13 1 0 2.544654 -1.603899 2.138717
14 1 0 0.651704 -0.199506 1.325489
15 1 0 2.462525 -0.080409 -2.615093
16 1 0 1.403688 3.037533 -1.378509
17 1 0 -0.104305 2.994013 -0.334690
18 1 0 2.854380 1.328196 2.207983
19 55 0 -2.402151 -0.280109 -0.240410
20 9 0 -1.066437 -0.356162 2.344842
Int1-CsF
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
1 6 0 3.373625 -1.696071 -0.911110
2 6 0 3.734536 -1.337678 0.441380
3 6 0 2.953460 -0.478618 1.138260
4 6 0 1.676762 0.063869 0.597233
5 6 0 1.387172 -0.242209 -0.855110
6 6 0 2.266522 -1.192016 -1.526114
7 6 0 1.440805 1.498290 1.052607
8 6 0 1.403296 2.572084 0.302669
9 6 0 1.345940 3.660351 -0.426885
10 8 0 0.393626 0.236882 -1.435962
11 1 0 4.019558 -2.383372 -1.454416
12 1 0 4.636502 -1.756826 0.878454
13 1 0 3.220751 -0.190435 2.153022
14 1 0 0.841121 -0.539511 1.141869
15 1 0 2.022034 -1.447598 -2.553977
16 1 0 1.321945 1.616506 2.131204
17 1 0 2.238238 4.241115 -0.657257
18 1 0 0.405611 4.022282 -0.841662
19 55 0 -2.461266 -0.215648 -0.088457
20 9 0 -0.441987 -1.187174 1.853110
Ts2a-CsF
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
1 6 0 3.523121 -1.496506 -0.854265
2 6 0 3.853430 -1.035721 0.471684
3 6 0 3.004064 -0.198603 1.118331
4 6 0 1.691099 0.194496 0.554190
5 6 0 1.434637 -0.188202 -0.878164
6 6 0 2.381036 -1.110236 -1.493202
7 6 0 1.255747 1.576842 1.005428
8 6 0 0.926281 2.606663 0.263961
9 6 0 0.586661 3.661266 -0.438099
10 8 0 0.415450 0.195304 -1.489853
11 1 0 4.218745 -2.163087 -1.360904
12 1 0 4.784263 -1.355801 0.931286
13 1 0 3.247031 0.170580 2.112973
14 1 0 0.916107 -0.523402 1.112308
15 1 0 2.159851 -1.438152 -2.505750
16 1 0 1.243857 1.707725 2.089572
17 1 0 1.326745 4.388002 -0.771114
18 1 0 -0.445874 3.847395 -0.732719
19 55 0 -2.377750 -0.341927 -0.061589
20 9 0 -0.214950 -1.272191 1.770156
Int2a
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
1 6 0 -3.815948 -1.750022 0.000282
2 6 0 -4.526537 -0.543758 -0.139883
3 6 0 -3.807863 0.651628 -0.141779
4 6 0 -2.405381 0.689114 -0.012976
5 6 0 -1.657052 -0.541079 0.129889
6 6 0 -2.431795 -1.748776 0.132249
7 6 0 -1.748303 1.996402 -0.026488
8 6 0 -0.474283 2.346164 0.047496
9 6 0 0.731310 2.867534 0.111973
10 8 0 -0.372409 -0.551807 0.246370
11 1 0 -4.354109 -2.697381 0.006273
12 1 0 -5.608679 -0.540406 -0.242578
13 1 0 -4.342823 1.595853 -0.247913
14 1 0 -1.888397 -2.686211 0.241792
15 1 0 -2.437049 2.842409 -0.112756
16 1 0 1.196774 3.130686 1.063965
17 1 0 1.324407 3.067144 -0.783098
18 55 0 2.543714 -0.438198 -0.045477
HF
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
1 9 0 0.000000 0.000000 0.094093
2 1 0 0.000000 0.000000 -0.846840
Ts3a-CsF
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
1 6 0 3.134759 -2.237653 0.168006
2 6 0 4.264251 -1.425863 -0.040090
3 6 0 4.102774 -0.042097 -0.163676
4 6 0 2.823197 0.519746 -0.081137
5 6 0 1.665934 -0.293193 0.125830
6 6 0 1.850932 -1.693072 0.251461
7 6 0 2.454981 1.913892 -0.179011
8 6 0 1.189457 2.317366 -0.075665
9 6 0 0.180108 3.234523 -0.039705
10 8 0 0.526613 0.343008 0.182218
11 1 0 3.261336 -3.314188 0.268603
12 1 0 5.254100 -1.870416 -0.101682
13 1 0 4.968159 0.599449 -0.322202
14 1 0 -1.187085 2.541760 0.216195
15 1 0 0.990438 -2.337547 0.419560
16 1 0 3.210937 2.682199 -0.340422
17 1 0 -0.127285 3.697475 -0.981832
18 1 0 0.106405 3.878481 0.841347
19 55 0 -2.382546 -0.769005 -0.083279
20 9 0 -2.183140 2.212459 0.369659
ProductA
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
1 6 0 -2.547110 -0.796004 0.000076
2 6 0 -2.639062 0.610309 0.000082
3 6 0 -1.496763 1.412412 0.000047
4 6 0 -0.238999 0.786836 -0.000066
5 6 0 -0.183590 -0.620655 -0.000117
6 6 0 -1.305809 -1.440212 -0.000008
7 6 0 1.137807 1.224111 -0.000163
8 6 0 1.908778 0.102522 -0.000001
9 8 0 1.124289 -1.039460 -0.000154
10 1 0 -3.455759 -1.391851 0.000120
11 1 0 -3.620487 1.077368 0.000096
12 1 0 -1.579891 2.496147 0.000075
13 1 0 -1.219829 -2.522607 0.000118
14 1 0 1.505509 2.241825 -0.000120
15 6 0 3.379099 -0.120855 0.000175
16 1 0 3.901931 0.839450 0.000416
17 1 0 3.693905 -0.687791 0.885252
18 1 0 3.694211 -0.687651 -0.884870
Ts2b-CsF
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
1 6 0 -4.292014 -2.028152 -0.680898
2 6 0 -2.934803 -2.352432 -0.389196
3 6 0 -2.080470 -1.395071 0.119039
4 6 0 -2.580642 -0.074602 0.399506
5 6 0 -4.028641 0.095696 0.345948
6 6 0 -4.855783 -0.798494 -0.366352
7 6 0 -1.616069 1.041602 0.045307
8 6 0 -1.908822 2.246169 -0.382967
9 6 0 -2.177623 3.462884 -0.796835
10 8 0 -4.388176 0.987162 1.231497
11 1 0 -4.925722 -2.793526 -1.124388
12 1 0 -2.567568 -3.346119 -0.629635
13 1 0 -1.005525 -1.553479 0.213158
14 1 0 -3.068263 0.627610 1.527937
15 1 0 -5.915484 -0.598998 -0.496819
16 1 0 -0.572739 0.714672 0.164200
17 1 0 -2.295791 3.699437 -1.854657
18 1 0 -2.304187 4.290965 -0.098257
19 55 0 3.782878 -0.093522 -0.014675
20 9 0 0.950177 -0.553306 0.388031
Int2b-CsF
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
1 6 0 -3.498067 -2.478065 0.317453
2 6 0 -4.253566 -1.841383 -0.674494
3 6 0 -3.974981 -0.510988 -0.987452
4 6 0 -2.958639 0.218589 -0.338054
5 6 0 -2.160600 -0.451563 0.632027
6 6 0 -2.465909 -1.787971 0.954317
7 6 0 -2.818569 1.644110 -0.685691
8 6 0 -2.160935 2.604813 -0.066254
9 6 0 -1.546642 3.619536 0.487472
10 8 0 -1.147957 0.147226 1.288992
11 1 0 -3.704076 -3.511526 0.587155
12 1 0 -5.052318 -2.368704 -1.189543
13 1 0 -4.573178 -0.002964 -1.741995
14 1 0 -0.412889 0.588828 0.658463
15 1 0 -1.858547 -2.274071 1.713882
16 1 0 -3.389397 1.948738 -1.566377
17 1 0 -2.021094 4.220654 1.263198
18 1 0 -0.522926 3.878836 0.220658
19 55 0 3.266083 -0.339322 -0.136154
20 9 0 0.678995 0.989185 -0.067204
Ts3b-CsF
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
1 6 0 4.971356 -1.840729 -0.003600
2 6 0 3.682841 -2.393249 0.194328
3 6 0 2.582731 -1.557367 0.225760
4 6 0 2.730536 -0.147514 0.125596
5 6 0 4.052508 0.410893 -0.040050
6 6 0 5.153272 -0.476644 -0.163017
7 6 0 1.601844 0.714053 -0.011067
8 6 0 1.763556 2.085877 -0.107430
9 6 0 1.166056 3.220967 0.285454
10 8 0 4.218872 1.709963 -0.127492
11 1 0 5.835944 -2.499854 -0.037911
12 1 0 3.562505 -3.468035 0.296320
13 1 0 1.578922 -1.959837 0.333911
14 1 0 3.064420 2.163602 -0.386098
15 1 0 6.140477 -0.053884 -0.325950
16 1 0 0.617241 0.249631 -0.220119
17 1 0 0.467514 3.252885 1.123813
18 1 0 1.426905 4.180811 -0.156648
19 55 0 -3.879722 -0.190642 0.007984
20 9 0 -1.032042 -0.573046 -0.342484
Int3b-CsF
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
1 6 0 4.209083 -1.699845 0.081477
2 6 0 4.827158 -0.423448 -0.162667
3 6 0 4.054226 0.696550 -0.222809
4 6 0 2.615912 0.653425 -0.047214
5 6 0 1.964962 -0.676323 0.159356
6 6 0 2.858889 -1.823106 0.238881
7 6 0 1.927747 1.853109 -0.076195
8 6 0 0.525226 2.084693 0.115836
9 6 0 -0.043801 3.307530 -0.004669
10 8 0 0.724369 -0.828549 0.249631
11 1 0 4.839865 -2.584501 0.137203
12 1 0 5.903755 -0.364484 -0.290580
13 1 0 4.510642 1.668538 -0.397841
14 1 0 -0.100715 1.240251 0.362719
15 1 0 2.393804 -2.788959 0.415734
16 1 0 2.529426 2.744887 -0.262250
17 1 0 -1.121422 3.395547 0.134488
18 1 0 0.542410 4.190285 -0.257246
19 55 0 -2.485839 -0.790047 -0.087075
20 9 0 -2.911997 2.082655 0.273096
Ts4b-CsF
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
1 6 0 -4.618681 -2.072508 0.138712
2 6 0 -3.223296 -2.410668 0.302464
3 6 0 -2.275701 -1.441727 0.200522
4 6 0 -2.631072 -0.050387 -0.057673
5 6 0 -4.067461 0.284524 -0.337866
6 6 0 -5.025611 -0.804998 -0.152713
7 6 0 -1.619584 0.869650 -0.027860
8 6 0 -1.701149 2.336093 -0.131891
9 6 0 -2.026229 3.167309 0.866014
10 8 0 -4.433493 1.402648 -0.740180
11 1 0 -5.360166 -2.862690 0.242340
12 1 0 -2.947935 -3.439617 0.516231
13 1 0 -1.217333 -1.655632 0.334367
14 1 0 -1.350263 2.753921 -1.079454
15 1 0 -6.074876 -0.562001 -0.297105
16 1 0 -0.602005 0.455288 0.093794
17 1 0 -2.352702 2.799124 1.835950
18 1 0 -1.983318 4.245260 0.733894
19 55 0 3.845085 -0.134255 -0.074257
20 9 0 1.001064 -0.537168 0.314145
Int4b-CsF
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
1 6 0 -4.252175 -2.371738 -0.051768
2 6 0 -2.823013 -2.482647 0.063683
3 6 0 -2.057236 -1.355673 0.109622
4 6 0 -2.636393 -0.021260 0.045437
5 6 0 -4.117387 0.094474 -0.089672
6 6 0 -4.867046 -1.155627 -0.122559
7 6 0 -1.710305 1.010441 0.128728
8 6 0 -1.758711 2.459187 0.126803
9 6 0 -2.795683 3.321715 -0.002101
10 8 0 -4.719538 1.188236 -0.175503
11 1 0 -4.850647 -3.280416 -0.083996
12 1 0 -2.364951 -3.466573 0.115904
13 1 0 -0.971602 -1.404490 0.199024
14 1 0 -0.768935 2.900753 0.248175
15 1 0 -5.946442 -1.067233 -0.212306
16 1 0 -0.685090 0.633148 0.225447
17 1 0 -3.812351 2.975277 -0.131053
18 1 0 -2.601064 4.392047 0.023328
19 55 0 3.867259 -0.077870 -0.057627
20 9 0 1.018429 -0.433197 0.326664
Ts5b-CsF
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
1 6 0 -4.683454 -2.043440 -0.363788
2 6 0 -3.504244 -2.440726 0.325184
3 6 0 -2.562534 -1.488439 0.635698
4 6 0 -2.762715 -0.095458 0.368422
5 6 0 -4.047655 0.328064 -0.216939
6 6 0 -4.911663 -0.724980 -0.687840
7 6 0 -1.625648 0.749045 0.306729
8 6 0 -1.720290 2.124007 0.054566
9 6 0 -2.869540 2.828813 0.372477
10 8 0 -4.430241 1.541512 -0.355578
11 1 0 -5.417712 -2.795881 -0.644918
12 1 0 -3.334267 -3.488172 0.557402
13 1 0 -1.614484 -1.778815 1.081860
14 1 0 -0.914477 2.614158 -0.490261
15 1 0 -5.815942 -0.422748 -1.208728
16 1 0 -0.635367 0.270156 0.285569
17 1 0 -3.440531 2.579221 1.255262
18 1 0 -3.043199 3.824378 -0.031193
19 55 0 4.021377 -0.083057 -0.098659
20 9 0 1.178737 -0.443061 0.299869
Product B
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
1 6 0 2.453041 -0.719305 0.034128
2 6 0 2.488809 0.678640 0.095762
3 6 0 1.294560 1.402169 0.054681
4 6 0 0.056334 0.748622 -0.035796
5 6 0 0.043054 -0.662553 -0.079512
6 6 0 1.231048 -1.393766 -0.057264
7 6 0 -1.225483 1.445898 -0.139135
8 6 0 -2.371653 0.758075 -0.014929
9 6 0 -2.325279 -0.715506 0.287099
10 8 0 -1.136366 -1.347405 -0.232475
11 1 0 3.377436 -1.290382 0.060552
12 1 0 3.439201 1.199852 0.169206
13 1 0 1.313567 2.489623 0.084895
14 1 0 -3.344728 1.237067 -0.086813
15 1 0 1.187597 -2.477906 -0.109707
16 1 0 -1.222302 2.517169 -0.327188
17 1 0 -2.370311 -0.896903 1.374756
18 1 0 -3.156114 -1.252926 -0.176113
S1