Supporting Information s21

Supporting Information

Microsolvation effect on the reactivity of oxy-nucleophiles: the case of the gas-phase SN2 reactions of YO- (CH3OH)n=1,2 towards CH3Cl

Liu Yun-Yun1 Qiu Fang-Zhou1 Zhu Jun2 Ren Yi*1 Lau Kai-Chung *3

1 College of Chemistry and Key State Laboratory of Biotherapy, Sichuan University,

Chengdu 610064, China

2 State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry and Department of Chemistry, Xiamen University, Xiamen 361005, China

3Department of Biology and Chemistry, City University of Hong Kong,

Kowloon, Hong Kong

*E-mail: ;

Table S1. MP2/6-31+G(d) geometries and NPA charges of methanol-microsolvated nucleophiles, Nu(CH3OH)n=1,2, and hydrides of nucleophiles, NuH(CH3OH)n=1,2 (Nu = HO, CH3O, C2H5O, FC2H4O, ClC2H4O, HOO, CH3OO, FO, ClO, BrO).

BrO-(CH3OH)
Atomic Number / Charge / X / Y / Z
O / -0.97159 / 0.002627 / 1.004632 / 0.446898
Br / 0.02997 / 1.303282 / -0.173359 / -0.052963
O / -0.86702 / -2.342103 / 0.423429 / -0.597926
H / 0.54203 / -1.403455 / 0.679727 / -0.283877
C / -0.07735 / -2.787982 / -0.57873 / 0.29268
H / 0.11456 / -2.842193 / -0.215381 / 1.329907
H / 0.10806 / -3.793009 / -0.88656 / -0.020905
H / 0.12133 / -2.132528 / -1.462337 / 0.280719
BrOH(CH3OH)
Atomic Number / Charge / X / Y / Z
O / -0.80251 / 2.154446 / 0.287426 / 0.613464
H / 0.47741 / 2.016454 / -0.295317 / 1.381098
O / -0.7993 / -0.254735 / 1.295806 / -0.283889
H / 0.52382 / 0.639568 / 1.036148 / 0.070857
Br / 0.25173 / -1.239349 / -0.247875 / 0.019906
C / -0.09832 / 2.783408 / -0.46936 / -0.440143
H / 0.15945 / 2.902587 / 0.222275 / -1.272568
H / 0.14247 / 3.765718 / -0.828188 / -0.121507
H / 0.14525 / 2.15475 / -1.30897 / -0.750341
C2H5O-(CH3OH)
Atomic Number / Charge / X / Y / Z
O / -1.03573 / -0.460943 / -0.471252 / -0.760915
C / 0.09484 / -1.322878 / -0.50462 / 0.312701
H / 0.06727 / -0.820323 / -0.239848 / 1.276105
O / -0.8969 / 1.665081 / 0.792255 / -0.134492
H / 0.54705 / 0.761986 / 0.325049 / -0.427367
C / -0.07172 / 2.533139 / -0.239441 / 0.267217
H / 0.10919 / 2.725195 / -0.963339 / -0.54166
H / 0.10088 / 3.493825 / 0.2048 / 0.563573
H / 0.10666 / 2.140503 / -0.807219 / 1.127724
H / 0.06063 / -1.754398 / -1.522394 / 0.477008
C / -0.51651 / -2.508763 / 0.463327 / 0.151733
H / 0.15634 / -2.129427 / 1.486487 / 0.051476
H / 0.15089 / -3.058537 / 0.213557 / -0.763208
H / 0.1271 / -3.200915 / 0.419291 / 1.009696
C2H5OH (CH3OH)
Atomic Number / Charge / X / Y / Z
C / -0.09559 / 2.852581 / -0.515097 / 0.211304
H / 0.13778 / 3.84928 / -0.206656 / 0.540342
H / 0.15773 / 2.361093 / -1.065475 / 1.01209
H / 0.1409 / 2.929492 / -1.156145 / -0.671945
O / -0.79747 / 2.020195 / 0.630327 / -0.04653
O / -0.82786 / -0.648364 / -0.267259 / -0.553047
H / 0.50186 / 0.244766 / 0.097346 / -0.378826
H / 0.47105 / 2.414587 / 1.151983 / -0.766933
C / 0.06465 / -1.579712 / 0.369873 / 0.325418
H / 0.12221 / -1.596853 / 1.453989 / 0.143993
H / 0.12227 / -1.289532 / 0.20832 / 1.373349
C / -0.5165 / -2.944827 / -0.229015 / 0.059103
H / 0.16797 / -3.700962 / 0.228417 / 0.706135
H / 0.17574 / -3.228981 / -0.065033 / -0.983844
H / 0.17525 / -2.92579 / -1.305845 / 0.247305
ClC2H4O-(CH3OH)
Atomic Number / Charge / X / Y / Z
O / -1.02688 / -0.788118 / 1.189239 / 0.011309
C / 0.07195 / 0.25073 / 0.471641 / 0.55444
H / 0.08485 / -0.01875 / -0.57165 / 0.839061
O / -0.88564 / -2.663227 / -0.421661 / -0.745832
H / 0.54488 / -1.892793 / 0.23599 / -0.512578
C / -0.07412 / -3.475229 / -0.506287 / 0.403695
H / 0.11312 / -3.874922 / 0.475181 / 0.702858
H / 0.10626 / -4.320669 / -1.169893 / 0.180836
H / 0.10973 / -2.932559 / -0.92088 / 1.268708
H / 0.08137 / 0.684886 / 0.938252 / 1.466695
C / -0.25083 / 1.357473 / 0.388543 / -0.497406
H / 0.16969 / 0.998317 / -0.147083 / -1.37661
H / 0.16547 / 1.681924 / 1.391609 / -0.775848
Cl / -0.20985 / 2.852204 / -0.499738 / 0.07757
ClC2H4OH(CH3OH)
Atomic Number / Charge / X / Y / Z
C / 0.03976 / 1.220112 / 1.336769 / -0.376554
H / 0.15178 / 1.878519 / 2.212117 / -0.332192
H / 0.14559 / 0.984427 / 1.140405 / -1.430909
O / -0.81672 / 0.058839 / 1.664599 / 0.36561
H / 0.51273 / -0.687704 / 1.109119 / 0.046385
C / -0.29501 / 1.98674 / 0.170372 / 0.219562
H / 0.19102 / 2.122017 / 0.32305 / 1.291085
H / 0.1828 / 2.957579 / 0.05155 / -0.267819
O / -0.80776 / -1.932066 / -0.113962 / -0.520256
H / 0.48546 / -1.426665 / -0.93966 / -0.40927
C / -0.09412 / -3.134606 / -0.187683 / 0.263339
H / 0.15462 / -3.646986 / 0.762616 / 0.119515
H / 0.13828 / -3.777603 / -1.001719 / -0.084514
H / 0.13989 / -2.906767 / -0.320309 / 1.32582
Cl / -0.12833 / 1.120913 / -1.391707 / 0.020058
ClO-(CH3OH)
Atomic Number / Charge / X / Y / Z
O / -0.91353 / -0.692541 / 0.903055 / 0.416523
O / -0.87154 / 1.738337 / 0.538591 / -0.494549
H / 0.54125 / 0.7688 / 0.721679 / -0.207864
Cl / -0.02007 / -1.702905 / -0.355403 / -0.116617
C / -0.07779 / 2.158787 / -0.58731 / 0.246506
H / 0.10637 / 3.214834 / -0.773042 / 0.013618
H / 0.11583 / 2.063726 / -0.425994 / 1.330801
H / 0.11947 / 1.582937 / -1.4901 / -0.008895
ClOH(CH3OH)
Atomic Number / Charge / X / Y / Z
O / -0.80437 / 1.632612 / 0.513878 / 0.43674
H / 0.47762 / 1.690223 / 0.292371 / 1.382802
O / -0.72904 / -0.958174 / 1.030342 / -0.364529
H / 0.52533 / -0.009315 / 0.936633 / -0.08175
Cl / 0.18039 / -1.636564 / -0.471704 / 0.101948
C / -0.09715 / 2.254652 / -0.535339 / -0.331213
H / 0.14543 / 1.755815 / -1.494163 / -0.164679
H / 0.15958 / 2.144409 / -0.24516 / -1.374843
H / 0.1422 / 3.317052 / -0.612446 / -0.085051
FC2H4O-(CH3OH)
Atomic Number / Charge / X / Y / Z
O / -1.03408 / -0.196099 / 1.028711 / -0.264173
C / 0.04869 / 0.776568 / 0.401724 / 0.490465
H / 0.08244 / 0.4247 / -0.525974 / 0.997418
O / -0.8891 / -2.202096 / -0.540811 / -0.627722
H / 0.54612 / -1.366886 / 0.082175 / -0.543982
C / -0.07328 / -3.059541 / -0.202104 / 0.437632
H / 0.1118 / -3.361717 / 0.856784 / 0.408356
H / 0.10463 / -3.964259 / -0.820163 / 0.364973
H / 0.10863 / -2.597485 / -0.386332 / 1.421504
H / 0.07699 / 1.20183 / 1.04794 / 1.290725
C / 0.18048 / 1.916205 / 0.009522 / -0.438003
H / 0.12086 / 1.575726 / -0.712789 / -1.183222
H / 0.11664 / 2.334559 / 0.892773 / -0.926074
F / -0.50084 / 3.015522 / -0.621386 / 0.262766
FC2H4OH(CH3OH)
Atomic Number / Charge / X / Y / Z
C / 0.01148 / 1.625082 / 0.762292 / -0.338903
H / 0.154 / 2.544274 / 1.349068 / -0.231417
H / 0.14579 / 1.412363 / 0.65444 / -1.411534
O / -0.81197 / 0.598566 / 1.479133 / 0.327806
H / 0.5109 / -0.265458 / 1.107567 / 0.037735
C / 0.16214 / 1.867375 / -0.599269 / 0.264869
H / 0.14846 / 1.944925 / -0.544623 / 1.352153
H / 0.14058 / 2.742981 / -1.091941 / -0.167163
F / -0.47546 / 0.755715 / -1.454119 / -0.013488
O / -0.81576 / -1.64729 / 0.000772 / -0.519836
H / 0.49515 / -1.151652 / -0.830221 / -0.39558
C / -0.09226 / -2.851228 / -0.044194 / 0.260589
H / 0.15221 / -3.351758 / 0.910554 / 0.103641
H / 0.13727 / -3.506037 / -0.854102 / -0.07548
H / 0.13745 / -2.628648 / -0.165878 / 1.325958
FO-(CH3OH)
Atomic Number / Charge / X / Y / Z
O / -0.87792 / -1.212789 / -0.68577 / -0.359603
H / 0.53651 / -0.20975 / -0.740365 / -0.140185
O / -0.49994 / 1.327869 / -0.684523 / 0.332707
F / -0.42414 / 1.638012 / 0.667406 / -0.219458
C / -0.07628 / -1.670938 / 0.523035 / 0.208031
H / 0.11163 / -1.533203 / 0.545912 / 1.300345
H / 0.12759 / -1.150896 / 1.396584 / -0.211191
H / 0.10255 / -2.74327 / 0.615357 / -0.006868
FOH(CH3OH)
Atomic Number / Charge / X / Y / Z
O / -0.80685 / 1.185323 / -0.685366 / -0.22076
H / 0.47853 / 1.389542 / -0.830596 / -1.161232
O / -0.30059 / -1.509664 / -0.630729 / 0.326767
H / 0.51213 / -0.535774 / -0.723173 / 0.136998
C / -0.09681 / 1.811875 / 0.538707 / 0.215209
H / 0.14843 / 1.429649 / 1.39639 / -0.344664
H / 0.16025 / 1.551938 / 0.647045 / 1.266883
H / 0.14221 / 2.897919 / 0.469471 / 0.113051
F / -0.2373 / -1.667755 / 0.704154 / -0.238927
HOO-(CH3OH)
Atomic Number / Charge / X / Y / Z
O / -1.05982 / -0.864207 / 0.000012 / -0.591002
H / 0.51023 / 0.542883 / 0.83651 / -0.172792
O / -0.56029 / 1.498605 / -0.72226 / 0.102321
H / 0.51022 / 0.542967 / -0.836577 / -0.17281
O / -0.56029 / 1.498548 / 0.722277 / 0.102332
C / -0.03849 / -1.90087 / -0.000015 / 0.285584
H / 0.06435 / -2.576849 / 0.888692 / 0.179797
H / 0.06435 / -2.576922 / -0.888649 / 0.179647
H / 0.06975 / -1.590431 / -0.000118 / 1.363442
HOOH(CH3OH)
Atomic Number / Charge / X / Y / Z
O / -0.8065 / 1.410955 / -0.767087 / -0.048501
H / 0.48805 / 0.456118 / -0.719284 / 0.144324
O / -0.45927 / -1.656554 / 0.775966 / -0.132509
H / 0.47245 / -2.313628 / 1.018888 / 0.551015
O / -0.48282 / -1.546132 / -0.665801 / 0.148758
H / 0.47848 / -1.86443 / -1.02331 / -0.7056
C / -0.08894 / 1.95253 / 0.552076 / 0.025093
H / 0.12538 / 1.884175 / 0.962691 / 1.039897
H / 0.14299 / 3.004347 / 0.469253 / -0.250843
H / 0.13018 / 1.452086 / 1.234686 / -0.671332
CH3O-(CH3OH)
Atomic Number / Charge / X / Y / Z
O / -1.03473 / 1.120365 / -0.378088 / 0.595071
C / -0.05036 / 1.951118 / 0.316106 / -0.263932
H / 0.06502 / 2.820034 / -0.285303 / -0.62333
H / 0.07504 / 1.433892 / 0.668989 / -1.187539
H / 0.06433 / 2.396474 / 1.229119 / 0.19802
O / -0.90399 / -1.181921 / -0.617605 / -0.414079
H / 0.54646 / -0.192388 / -0.574749 / -0.000252
C / -0.07093 / -1.893048 / 0.457913 / 0.143577
H / 0.10529 / -1.969872 / 0.387848 / 1.242113
H / 0.1052 / -1.430865 / 1.433482 / -0.087102
H / 0.09868 / -2.913244 / 0.462047 / -0.267709
CH3OH(CH3OH)
Atomic Number / Charge / X / Y / Z
C / -0.09607 / 2.205302 / -0.397464 / 0.228547
H / 0.1379 / 3.182233 / 0.014889 / 0.497459
H / 0.1577 / 1.779352 / -0.910194 / 1.089561
H / 0.14103 / 2.310663 / -1.106953 / -0.597562
O / -0.79806 / 1.278507 / 0.653023 / -0.10169
O / -0.81715 / -1.31556 / -0.48606 / -0.489111
H / 0.49931 / -0.451535 / -0.045121 / -0.355429
H / 0.4711 / 1.614262 / 1.138252 / -0.875303
C / -0.08873 / -2.28437 / 0.164804 / 0.329898
H / 0.12493 / -2.409422 / 1.219263 / 0.053626
H / 0.14303 / -3.230034 / -0.354499 / 0.169174
H / 0.12502 / -2.024687 / 0.104624 / 1.394212
CH3OO-(CH3OH)
Atomic Number / Charge / X / Y / Z
O / -0.89218 / -1.55931 / 0.122644 / 0.780549
H / 0.54153 / -0.67463 / 0.593503 / 0.481226
O / -0.50594 / 1.17128 / -0.082362 / -0.67175
O / -0.66998 / 0.63773 / 1.175598 / -0.095662
C / -0.07444 / 1.96731 / -0.631731 / 0.350423
H / 0.10349 / 2.38012 / -1.570222 / -0.050405
H / 0.11462 / 2.7854 / 0.052975 / 0.6201
H / 0.12628 / 1.36709 / -0.839201 / 1.247468
C / -0.07812 / -2.12873 / -0.413042 / -0.394453
H / 0.10265 / -2.50745 / 0.371905 / -1.07071
H / 0.13232 / -1.40301 / -1.015771 / -0.958695
H / 0.09977 / -2.97658 / -1.051594 / -0.109905
CH3OOH(CH3OH)
Atomic Number / Charge / X / Y / Z
O / -0.80995 / -1.631857 / -0.788127 / -0.252283
H / 0.48837 / -0.751163 / -0.447866 / -0.502722
O / -0.37039 / 1.164206 / -0.011052 / -0.559823
O / -0.46858 / 1.074509 / 1.276707 / 0.157538
C / -0.10312 / 1.815246 / -0.899857 / 0.356397
H / 0.16599 / 1.821514 / -1.857152 / -0.16907
H / 0.15056 / 2.833087 / -0.55739 / 0.558594
H / 0.16246 / 1.237804 / -0.977173 / 1.280519
C / -0.0881 / -2.415009 / 0.305597 / 0.227792
H / 0.13081 / -1.930688 / 0.810175 / 1.071751
H / 0.1258 / -2.612644 / 1.04046 / -0.562146
H / 0.14254 / -3.363979 / -0.116442 / 0.560895
H / 0.47362 / 1.509792 / 1.850722 / -0.506409
BrO-(CH3OH)2
Atomic Number / Charge / X / Y / Z
O / -0.85456 / -1.414786 / -0.068339 / 2.314909
H / 0.53731 / -0.985116 / -0.446954 / 1.484479
O / -0.85456 / -1.414786 / -0.068339 / -2.314909
H / 0.53731 / -0.985116 / -0.446954 / -1.484479
O / -0.99397 / -0.301085 / -0.812225 / 0
C / -0.0812 / -1.414786 / 1.337477 / 2.145442
H / 0.11535 / -2.07092 / 1.654359 / 1.321659
H / 0.11345 / -1.785839 / 1.783858 / 3.074816
H / 0.12689 / -0.406153 / 1.725899 / 1.946322
C / -0.0812 / -1.414786 / 1.337477 / -2.145442
H / 0.12689 / -0.406153 / 1.725899 / -1.946322
H / 0.11345 / -1.785839 / 1.783858 / -3.074816
H / 0.11535 / -2.07092 / 1.654359 / -1.321659
Br / 0.07948 / 1.500535 / -0.511223 / 0
BrOH(CH3OH)2
Atomic Number / Charge / X / Y / Z
O / -0.81306 / -1.654763 / -1.274964 / -0.770197
H / 0.48248 / -0.718294 / -1.279973 / -1.043891
O / -0.84283 / -1.612016 / 1.201896 / 0.451542
H / 0.52006 / -1.846443 / 0.412344 / -0.093284
O / -0.80245 / 0.691831 / 0.163588 / 1.388783
H / 0.53308 / -0.146526 / 0.652066 / 1.118262
Br / 0.23939 / 1.555797 / -0.061578 / -0.235308
C / -0.0927 / -1.636832 / 2.381638 / -0.365236
H / 0.14049 / -2.64655 / 2.56599 / -0.744014
H / 0.15206 / -1.336551 / 3.210983 / 0.274923
H / 0.13841 / -0.936279 / 2.2983 / -1.202984
C / -0.10265 / -1.80327 / -2.224612 / 0.306249
H / 0.15264 / -2.842494 / -2.156722 / 0.625855
H / 0.14055 / -1.598615 / -3.239396 / -0.046528
H / 0.15451 / -1.140932 / -1.974687 / 1.140346
ClC2H4O-(CH3OH)2
Atomic Number / Charge / X / Y / Z
C / -0.25962 / -1.596727 / -0.13493 / 0.525065
H / 0.17359 / -1.407994 / -0.888734 / 1.290346
H / 0.16819 / -1.608313 / 0.858716 / 0.97489
C / 0.06341 / -0.525107 / -0.206546 / -0.558658
H / 0.09929 / -0.57018 / -1.212533 / -1.024773
H / 0.10333 / -0.77709 / 0.524224 / -1.353349
O / -1.03248 / 0.695406 / 0.057188 / 0.041724
O / -0.86953 / 1.64181 / 2.406143 / -0.638017
H / 0.54315 / 1.32814 / 1.458453 / -0.424797
O / -0.87245 / 1.900829 / -2.161032 / 0.75681