Directory UMM :wiley:Public:journals:jcc:suppmat:19:
Supplementary Material for
Methane Activation by Mercury(II) Complexes
Contribution from the Department of Chemistry
University of Memphis
Memphis, TN 38152
by
Thomas R.Cundari and Akihiko Yoshikawa
Tables of Cartesian coordinates (in Å
) are given for all optimized geometries determined in
this study (16 pages). Enthalpic data are also given. Ordering information is given on any current
masthead page.
June 9, 1998
Cartesian Coordinates (in Å) for Optimized Stationary Points
0.000
0.000
0.000
HgH2
0.000
0.000
0.000
0.000
-1.690
1.690
Hg(1)
F(2)
F(3)
0.000
0.000
0.000
HgF2
0.000
0.000
0.000
0.000
-1.954
1.954
Hg(1)
Cl(2)
Cl(3)
0.000
0.000
0.000
HgCl2
0.000
0.000
0.000
0.000
-2.327
2.327
Hg(1)
Br(2)
Br(3)
0.000
0.000
0.000
HgBr2
0.000
0.000
0.000
0.000
-2.454
2.454
Hg(1)
I(2)
I(3)
0.000
0.000
0.000
HgI2
0.000
0.000
0.000
0.000
-2.642
2.642
Hg(1)
C(2)
C(3)
N(4)
N(5)
0.000
0.000
0.000
0.000
0.000
Hg(CN)2
0.000
0.000
0.000
0.000
0.000
0.000
-2.067
2.067
-3.221
3.221
Hg(1)
N(2)
N(3)
C(4)
C(5)
0.000
0.000
0.000
0.000
0.000
Hg(NC)2
0.000
0.000
0.000
0.000
0.000
0.000
-2.004
2.004
-3.176
3.176
0.000
0.000
0.000
Hg(NCS)2
0.000
0.000
0.000
0.000
-1.998
1.998
Hg(1)
H(2)
H(3)
Hg(1)
N(2)
N(3)
C(4)
C(5)
S(6)
S(7)
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
-3.173
3.173
-4.785
4.785
0.000
-2.413
2.413
-2.621
2.621
-2.777
2.777
Hg(SCN)2
0.000
0.000
0.000
1.644
-1.644
2.748
-2.748
-0.352
-0.374
-0.374
0.075
0.075
0.374
0.374
0.000
-2.051
2.051
-2.425
2.425
-2.425
2.425
Hg(NH2)2
0.000
0.000
0.000
-0.491
0.491
-0.491
0.491
0.000
0.000
0.000
0.807
-0.807
-0.807
0.807
Hg(1)
O(2)
O(3)
H(4)
H(5)
0.000
-1.989
1.989
-2.341
2.341
Hg(OH)2
0.000
0.103
-0.103
0.762
-0.762
-0.231
-0.300
-0.300
0.300
0.300
Hg(1)
S(2)
S(3)
H(4)
H(5)
0.000
-2.384
2.384
-2.476
2.476
Hg(SH)2
0.000
0.153
-0.153
1.112
-1.112
-0.443
-0.468
-0.468
0.468
0.468
Hg(1)
C(2)
C(3)
H(4)
H(5)
H(6)
H(7)
H(8)
H(9)
-0.257
-0.257
-0.257
-0.770
-0.770
0.770
-0.770
-0.770
0.770
Hg(CH3)2
0.000
0.000
0.000
0.889
-0.889
0.000
0.889
-0.889
0.000
0.000
-2.153
2.153
2.546
2.546
-2.546
-2.546
-2.546
2.546
Hg(1)
-0.309
Hg(CF3)2
0.000
0.000
Hg(1)
S(2)
S(3)
C(4)
C(5)
N(6)
N(7)
Hg(1)
N(2)
N(3)
H(4)
H(5)
H(6)
H(7)
C(2)
C(3)
F(4)
F(5)
F(6)
F(7)
F(8)
F(9)
Hg(1)
C(2)
C(3)
Cl(4)
Cl(5)
Cl(6)
Cl(7)
Cl(8)
Cl(9)
Hg(1)
C(2)
C(3)
C(4)
C(5)
H(6)
H(7)
H(8)
H(9)
H(10)
H(11)
H(12)
H(13)
H(14)
H(15)
Hg(1)
C(2)
C(3)
C(4)
C(5)
H(6)
H(7)
-0.309
-0.309
-0.928
-0.928
0.928
-0.928
-0.928
0.928
0.000
0.000
1.071
-1.071
0.000
1.071
-1.071
0.000
-2.166
2.166
2.684
2.684
-2.684
-2.684
-2.684
2.684
-0.419
-0.419
-0.419
-1.258
-1.258
1.258
-1.258
-1.258
1.258
Hg(CCl3)2
0.000
0.000
0.000
1.452
-1.452
0.000
1.452
-1.452
0.000
0.000
-2.170
2.170
2.789
2.789
-2.789
-2.789
-2.789
2.789
0.000
-2.162
2.162
-2.741
2.741
-2.534
2.534
-2.534
2.534
-3.843
3.843
-2.419
2.419
-2.419
2.419
cis-Hg(C2H5)2
0.000
0.000
0.000
0.000
0.000
-0.879
-0.879
0.879
0.879
0.000
0.000
-0.886
-0.886
0.886
0.886
-0.779
-0.727
-0.727
0.706
0.706
-1.274
-1.274
-1.274
-1.274
0.698
0.698
1.274
1.274
1.274
1.274
0.000
-2.166
2.166
-2.789
2.789
-2.524
2.524
trans-Hg(C2H5)2
0.000
0.053
-0.053
1.467
-1.467
-0.504
0.504
0.000
0.000
0.000
0.000
0.000
0.878
-0.878
H(8)
H(9)
H(10)
H(11)
H(12)
H(13)
H(14)
H(15)
Hg(1)
C(2)
H(3)
H(4)
H(5)
H(6)
-2.524
2.524
-3.891
3.891
-2.488
2.488
-2.488
2.488
-0.504
0.504
1.420
-1.420
2.047
-2.047
2.047
-2.047
-0.878
0.878
0.000
0.000
0.885
-0.885
-0.885
0.885
0.000
0.000
0.514
0.514
-1.028
0.000
HgMeH
0.000
0.000
-0.890
0.890
0.000
0.000
1.348
-0.803
-1.194
-1.194
-1.194
3.038
Hg(1)
F(2)
C(3)
H(4)
H(5)
H(6)
0.000
0.000
0.000
0.515
0.515
-1.031
HgMeF
0.000
0.000
0.000
-0.893
0.893
0.000
Hg(1)
Cl(2)
C(3)
H(4)
H(5)
H(6)
0.000
0.000
0.000
-0.516
-0.516
1.033
HgMeCl
0.000
0.000
0.000
-0.894
0.894
0.000
1.207
3.576
-0.919
-1.288
-1.288
-1.288
0.000
0.000
0.000
0.516
0.516
-1.033
HgMeBr
0.000
0.000
0.000
0.894
-0.894
0.000
1.193
3.687
-0.943
-1.313
-1.313
-1.312
Hg(1)
I(2)
C(3)
H(4)
H(5)
H(6)
0.000
0.000
0.000
0.516
0.516
-1.033
HgMeI
0.000
0.000
0.000
0.894
-0.894
0.000
1.167
3.844
-0.976
-1.345
-1.345
-1.345
Hg(1)
C(2)
C(3)
H(4)
H(5)
H(6)
N(7)
0.000
0.000
0.000
0.514
0.514
-1.029
0.000
HgMe(CN)
0.000
0.000
0.000
0.891
-0.891
0.000
0.000
0.607
2.721
-1.516
-1.897
-1.897
-1.897
3.878
0.000
0.000
0.000
HgMe(NC)
0.000
0.000
0.000
0.611
2.673
-1.502
Hg(1)
Br(2)
C(3)
H(4)
H(5)
H(6)
Hg(1)
N(2)
C(3)
1.260
3.256
-0.850
-1.222
-1.222
-1.222
H(4)
H(5)
H(6)
C(7)
0.515
0.515
-1.031
0.000
0.893
-0.893
0.000
0.000
-1.875
-1.875
-1.875
3.844
Hg(1)
N(2)
C(3)
H(4)
H(5)
H(6)
C(7)
S(8)
0.000
0.000
0.000
0.516
0.516
-1.032
0.000
0.000
HgMe(NCS)
0.000
0.000
0.000
0.894
-0.894
0.000
0.000
0.000
Hg(1)
S(2)
C(3)
H(4)
H(5)
H(6)
C(7)
N(8)
-0.126
2.331
-2.257
-2.610
-2.610
-2.654
2.518
2.654
HgMe(SCN)
1.143
1.114
1.212
1.738
1.738
0.190
-0.591
-1.738
0.000
0.000
0.000
-0.895
0.895
0.000
0.000
0.000
Hg(1)
N(2)
C(3)
H(4)
H(5)
H(6)
H(7)
H(8)
0.337
0.290
0.266
-0.772
0.772
0.772
0.743
0.743
HgMe(NH2)
-0.023
-2.088
2.105
2.466
2.504
2.504
-2.504
-2.504
0.000
0.000
0.000
0.000
-0.890
0.890
-0.809
0.809
Hg(1)
O(2)
C(3)
H(4)
H(5)
H(6)
H(7)
-0.143
-0.031
-0.148
-0.662
-0.662
0.883
-0.883
HgMe(OH)
0.018
2.038
-2.098
-2.478
-2.478
-2.475
2.478
0.000
0.000
0.000
-0.892
0.892
0.000
0.000
0.200
0.222
0.217
0.220
-0.673
HgMe(SH)
-0.027
2.387
-2.165
-2.546
-2.549
0.257
0.259
0.256
-0.773
0.773
Hg(1)
S(2)
C(3)
H(4)
H(5)
-0.078
1.992
-2.190
-2.559
-2.559
-2.559
3.164
4.790
H(6)
H(7)
1.111
-1.111
-2.536
2.549
0.773
0.259
Hg(1)
C(2)
C(3)
H(4)
H(5)
H(6)
F(7)
F(8)
F(9)
Hg(1)
C(2)
C(3)
H(4)
H(5)
H(6)
Cl(7)
Cl(8)
Cl(9)
Hg(1)
C(2)
C(3)
H(4)
H(5)
H(6)
C(7)
H(8)
H(9)
H(10)
H(11)
H(12)
Hg(1)
H(2)
H(3)
C(4)
H(5)
H(6)
H(7)
H(8)
0.000
0.000
0.000
0.515
0.515
-1.030
0.619
0.619
-1.237
HgMe(CF3)
0.000
0.000
0.000
0.892
-0.892
0.000
1.072
-1.072
0.000
-0.075
2.113
-2.206
-2.589
-2.589
-2.589
2.645
2.645
2.645
0.000
0.000
0.000
0.516
0.516
-1.032
0.839
0.839
-1.678
HgMe(CCl3)
0.000
0.000
0.000
0.893
-0.893
0.000
1.453
-1.453
0.000
-0.118
2.080
-2.245
-2.620
-2.620
-2.620
2.714
2.714
2.714
-0.621
-0.624
-0.631
0.358
-0.900
-1.360
0.773
-1.191
-1.190
1.359
1.360
0.698
HgMe(C2H5)
-0.484
1.556
-2.514
-2.803
-3.215
-2.639
2.179
1.586
2.173
1.614
2.205
3.215
0.074
-0.648
0.794
1.177
-0.011
1.608
-0.868
-1.590
0.066
-1.608
0.062
-1.236
-0.498
1.489
-1.489
-0.283
0.782
0.621
-0.863
-0.863
[HgH2·CH4]_
-0.897
-0.328
-2.218
1.584
0.502
2.218
1.849
1.849
0.000
0.000
0.000
0.000
0.000
0.000
-0.897
0.897
Hg(1)
F(2)
F(3)
C(4)
H(5)
H(6)
H(7)
H(8)
Hg(1)
Cl(2)
Cl(3)
C(4)
H(5)
H(6)
H(7)
H(8)
Hg(1)
Br(2)
Br(3)
C(4)
H(5)
H(6)
H(7)
H(8)
Hg(1)
I(2)
I(3)
C(4)
H(5)
H(6)
H(7)
H(8)
Hg(1)
C(2)
C(3)
C(4)
-0.561
1.673
-1.673
-0.175
0.826
0.642
-0.768
-0.768
[HgF2·CH4]_
-0.732
-0.166
-2.376
1.635
0.772
2.376
1.837
1.837
0.000
0.000
0.000
0.000
0.000
0.000
-0.900
0.900
-0.849
2.034
-2.034
-0.398
0.709
0.492
-0.961
-0.961
[HgCl2·CH4]_
-0.454
-0.043
-2.462
1.813
0.940
2.462
2.074
2.074
0.000
0.000
0.000
0.000
0.000
0.000
-0.904
0.904
-0.892
2.159
-2.159
-0.407
0.502
-0.964
-0.964
0.721
[HgBr2·CH4]_
-0.389
-0.083
-2.488
1.868
2.488
2.143
2.143
0.953
0.000
0.000
0.000
0.000
0.000
-0.904
0.904
0.000
-0.936
2.395
-2.395
-0.304
-1.380
0.124
0.124
0.750
[HgI2·CH4]_
-0.255
-0.121
-2.442
1.993
2.232
2.442
2.442
0.963
0.000
0.000
0.000
0.000
0.000
-0.903
0.903
0.000
-0.379
2.227
-1.607
0.038
[Hg(CN)2·CH4]_
-0.206
0.265
-1.880
2.109
0.000
0.000
0.000
-0.006
H(5)
H(6)
H(7)
H(8)
N(9)
N(10)
1.151
0.905
-0.546
-0.524
-2.316
2.316
1.273
2.791
2.348
2.356
-2.791
-0.900
-0.007
-0.021
-0.903
0.903
-0.002
0.013
Hg(1)
N(2)
N(3)
C(4)
H(5)
H(6)
H(7)
H(8)
C(9)
C(10)
Hg(1)
N(2)
N(3)
C(4)
H(5)
H(6)
H(7)
H(8)
C(9)
C(10)
S(11)
S(12)
-0.853
1.646
-1.804
-0.568
0.513
0.274
-1.147
-1.147
-2.378
2.378
[Hg(NC)2·CH4]_
-0.109
0.552
-1.894
2.203
1.413
2.917
2.420
2.420
-2.917
-0.370
0.000
0.000
0.000
0.000
0.000
0.000
0.905
-0.905
0.000
0.000
-1.293
1.274
-2.387
-0.708
0.279
0.214
-1.252
-1.252
-3.087
2.447
-4.048
4.048
[Hg(NCS)2·CH4]_
0.550
0.860
-1.151
2.786
1.868
3.393
3.077
3.077
-2.095
0.700
-3.393
0.476
0.000
0.000
0.000
0.000
0.000
0.000
0.905
-0.905
0.000
0.000
0.000
0.000
[Hg(SCN)2·CH4]_
Hg(1)
-1.667
0.786
0.000
S(2)
1.677
0.590
0.000
S(3)
-3.230
-1.030
0.000
C(4)
-0.623
2.819
0.000
H(5)
0.187
1.720
0.000
H(6)
0.396
3.242
0.000
H(7)
-1.103
3.200
-0.909
H(8)
-1.103
3.200
0.909
C(9)
-2.118
-2.338
0.000
N(10)
-1.403
-3.242
0.000
C(11)
2.637
1.995
0.000
N(12)
3.230
2.991
0.000
-1
There are two imaginary modes. The second one is 39 cm .
Hg(1)
N(2)
N(3)
C(4)
-0.090
1.851
-1.756
-0.197
[Hg(NH2)2·CH4]_
-0.756
0.255
-1.955
2.062
0.032
-0.062
-0.066
0.306
H(5)
H(6)
H(7)
H(8)
H(9)
H(10)
H(11)
H(12)
1.144
0.246
-0.468
-1.164
2.360
2.525
-1.594
-2.525
1.182
2.855
2.557
1.820
0.254
0.097
-2.855
-1.531
0.100
0.944
-0.649
0.800
-0.944
0.685
0.377
0.446
Hg(1)
O(2)
O(3)
C(4)
H(5)
H(6)
H(7)
H(8)
H(9)
H(10)
Hg(1)
S(2)
S(3)
C(4)
H(5)
H(6)
H(7)
H(8)
H(9)
H(10)
Hg(1)
C(2)
C(3)
C(4)
H(5)
H(6)
H(7)
H(8)
H(9)
H(10)
H(11)
H(12)
H(13)
H(14)
-0.749
1.414
-2.157
-0.410
0.667
0.312
-0.864
-1.186
2.157
-1.796
[Hg(OH)2·CH4]_
-0.485
0.136
-1.929
2.000
1.117
2.793
2.293
2.059
-0.010
-2.793
0.116
-0.184
0.292
0.088
-0.010
0.354
-0.870
0.870
0.409
0.086
-0.713
2.132
-2.211
-0.187
0.885
0.619
-0.377
-1.068
2.211
-1.259
[Hg(SH)2·CH4]_
-0.093
0.100
-1.947
2.231
1.269
2.893
2.470
2.505
0.129
-2.893
-0.169
0.026
-0.146
-0.313
-0.115
0.037
-1.368
0.288
1.368
-0.106
-0.308
2.134
-1.632
-0.232
0.881
0.579
-0.846
-0.846
2.468
2.468
2.674
-2.674
-1.448
-1.448
[Hg(CH3)2·CH4]_
-0.497
0.172
-2.172
2.033
1.013
2.783
2.230
2.230
-0.380
-0.380
1.135
-1.834
-2.783
-2.783
0.000
0.000
0.000
0.000
0.000
0.000
-0.894
0.894
-0.895
0.895
0.000
0.000
-0.892
0.892
Hg(1)
C(2)
C(3)
C(4)
H(5)
H(6)
H(7)
H(8)
F(9)
F(10)
F(11)
F(12)
F(13)
F(14)
Hg(1)
C(2)
C(3)
C(4)
H(5)
H(6)
H(7)
H(8)
Cl(9)
Cl(10)
Cl(11)
Cl(12)
Cl(13)
Cl(14)
Hg(1)
C(2)
C(3)
C(4)
H(5)
H(6)
H(7)
H(8)
H(9)
H(10)
C(11)
C(12)
-0.661
2.112
-1.676
-0.265
0.682
0.609
-0.844
-0.844
2.464
2.464
3.004
-3.004
-1.373
-1.373
[Hg(CF3)2·CH4]_
-0.198
0.319
-2.097
2.157
1.224
2.828
2.388
2.388
-0.440
-0.440
1.343
-1.948
-2.828
-2.828
0.000
0.000
0.000
0.000
0.000
0.000
-0.903
0.903
-1.077
1.077
0.000
0.000
-1.071
1.071
-0.797
2.100
-2.014
-0.465
0.597
-1.522
-0.458
-0.108
1.926
1.836
3.746
-3.746
-1.743
-1.602
[Hg(CCl3)2·CH4]_
-0.136
0.929
-1.952
2.306
1.634
2.126
2.760
3.020
-0.156
-0.197
1.564
-1.515
-2.825
-3.020
0.103
0.032
0.040
0.043
0.052
0.315
-0.955
0.797
-1.437
1.489
0.097
0.154
-1.489
1.403
-0.439
2.067
-1.723
-0.325
0.754
0.508
-0.932
-0.932
2.433
2.433
2.720
-3.231
[Hg(C2H5)2·CH4]_
-0.458
0.268
-2.180
2.068
1.015
2.792
2.279
2.279
0.823
0.823
-1.139
-1.861
0.000
0.000
0.000
0.000
0.000
0.000
-0.895
0.895
-0.882
0.882
0.000
0.000
H(13)
H(14)
H(15)
H(16)
H(17)
H(18)
H(19)
H(20)
-1.455
-1.455
-3.525
-3.525
-3.822
3.822
2.432
2.432
0.000
0.000
-2.776
-2.776
-1.283
-1.283
-2.792
-1.076
-1.725
-1.725
H2
0.000
0.000
H(1)
H(2)
0.374
-0.374
H(1)
F(2)
0.000
0.000
HF
0.000
0.000
-0.459
0.459
H(1)
Cl(2)
0.000
0.000
HCl
0.000
0.000
-0.639
0.639
0.000
0.000
HBr
0.000
0.000
-0.713
0.713
0.000
0.000
HI
0.000
0.000
-0.807
0.807
0.000
0.000
0.000
HCN
0.000
0.000
0.000
-1.113
-0.035
1.113
H(1)
N(2)
C(3)
0.000
0.000
0.000
HNC
0.000
0.000
0.000
-1.084
-0.083
1.084
H(1)
N(2)
C(3)
S(4)
-1.351
-0.345
0.336
1.351
HNCS
1.143
1.064
0.077
-1.143
0.000
0.000
0.000
0.000
H(1)
Br(2)
H(1)
I(2)
H(1)
C(2)
N(3)
HSCN
-0.881
0.881
-0.887
0.887
0.000
0.000
-0.886
0.886
H(1)
S(2)
C(3)
N(4)
N(1)
H(2)
H(3)
H(4)
O(1)
H(2)
H(3)
-1.070
0.247
0.714
1.070
-1.129
-1.375
0.279
1.375
0.000
0.000
0.000
0.000
-0.234
-0.700
-0.700
0.700
NH3
0.000
0.810
-0.810
0.000
0.200
-0.200
-0.200
-0.200
0.000
-0.756
0.756
H2O
0.000
0.000
0.000
-0.295
0.295
0.295
0.000
-0.982
0.982
H2S
0.000
0.000
0.000
-0.456
0.456
0.456
C(1)
H(2)
H(3)
H(4)
H(5)
0.000
0.634
-0.634
-0.634
0.634
CH4
0.000
-0.634
0.634
-0.634
0.634
0.000
-0.634
-0.634
0.634
0.634
C(1)
F(2)
F(3)
F(4)
H(5)
-0.310
-0.930
-0.930
0.930
-0.310
CHF3
0.000
1.074
-1.074
0.000
0.000
-0.314
-0.778
-0.778
-0.778
0.778
C(1)
Cl(2)
Cl(3)
Cl(4)
H(5)
-0.421
-1.263
-1.263
1.263
-0.421
CHCl3
0.000
1.458
-1.458
0.000
0.000
-0.276
-0.810
-0.810
-0.810
0.810
0.000
0.000
-0.888
0.888
0.000
0.888
-0.888
0.000
C2H6
0.000
0.000
-0.513
-0.513
-1.026
0.513
0.513
1.026
-0.769
0.769
-1.164
-1.164
1.164
1.164
1.164
-1.164
S(1)
H(2)
H(3)
C(1)
C(2)
H(3)
H(4)
H(5)
H(6)
H(7)
H(8)
Table S-2
Calculated Energetic Data for Reactants LsHgLaa
a.
b.
c.
La, Ls
-E(RHF)b
-E(MP2)b
H(298.15)c
H-
153.9363
154.0578
9.889
F-
200.5298
200.9831
5.246
Cl-
182.2664
182.6250
4.756
Br-
179.2043
179.5463
4.591
I-
175.3586
175.6719
4.533
CN-
183.1260
183.7646
14.931
NC-
183.0994
183.7182
14.307
NCS-
203.0209
203.8999
20.029
SCN-
203.0314
203.9039
19.570
NH2-
174.4438
174.8946
37.009
OH-
185.3198
185.8048
20.617
SH-
173.8965
174.2414
16.121
CH3-
167.2300
167.6005
50.302
CF3-
306.9647
308.2660
24.278
CCl3-
251.8310
252.9790
19.704
C2H5-
180.5159
181.1287
90.957
Pertinent calculated data for methane reactant are: E(RHF) = -7.8034 hartrees, E(MP2) =
-7.9278 hartrees, H(298.15K) = 31.911 kcal mol-1.
Total energies at the restricted Hartree Fock, E(RHF), and Moller-Plesset second order
perturbation theory, E(MP2), levels are reported in hartrees
This is the enthalpic correction (kcal mol-1), calculated using RHF-determined vibrational
frequencies, which includes the zero point energy and corrects enthalpies from 0 K to
298.15 K.
Table S-3
Calculated Energetic Data for Products LsHgCH3a
a.
b.
c.
Ls
-E(RHF)b
-E(MP2)b
H(298.15)c
H-
160.5833
160.8292
30.248
F-
183.8943
184.3059
28.294
Cl-
174.7596
175.1227
28.154
Br-
173.2255
173.5819
27.898
I-
171.3004
171.6424
27.827
CN-
175.1857
175.6893
33.006
NC-
175.1770
175.6720
32.931
NCS-
185.1412
185.7637
35.735
SCN-
185.1406
185.7615
35.588
NH2-
170.8393
171.2501
44.025
OH-
176.2817
176.7094
35.941
SH-
170.5667
170.9241
33.735
CH3-
167.2300
167.6005
50.302
CF3-
237.1016
237.9376
37.980
CCl3-
209.5363
210.2936
35.490
C2H5173.8729
174.3646
70.984
Pertinent calculated data for HLa products are given in Table S-4.
Total energies at the restricted Hartree Fock, E(RHF), and Moller-Plesset second order
perturbation theory, E(MP2), levels are reported in hartrees
This is the enthalpic correction (in kcal mol-1), calculated using RHF-determined
vibrational frequencies, which includes the zero point energy and corrects enthalpies from
0 K to 298.15 K.
Table S-4
Calculated Energetic Data for Products HLa
a
b.
La
-E(RHF)a
-E(MP2)a
H(298.15)b
H
1.1246
1.1405
8.583
F
24.4356
24.6033
8.339
Cl
15.2657
15.3937
6.652
Br
13.7232
13.8429
6.091
I
11.7917
11.8967
5.59
CN
15.7181
15.9828
13.391
NC
15.7025
15.9569
13.174
NCS
25.6597
26.0468
14.893
SCN
25.6564
26.0351
14.468
NH2
11.4099
11.5719
25.148
OH
16.8434
17.0223
16.555
SH
11.0920
11.2075
12.619
CH3
7.8034
7.9278
31.911
CF3
77.6781
78.2643
20.075
CCl3
50.1061
50.6100
16.968
C2H5
14.4519
14.6942
51.992
Total energies at the restricted Hartree Fock, E(RHF), and Moller-Plesset second order
perturbation theory, E(MP2), levels are reported in hartrees
This is the enthalpic correction (in kcal mol-1), calculated using RHF-determined
vibrational frequencies, which includes the zero point energy and corrects enthalpies from
0 K to 298.15 K.
Table S-5
Thermodynamic data for [LsHgLa·HtCH3]_
a.
b.
La,s
-E(RHF)a
-E(MP2)a
H(298.15)b
H-
161.5922
161.8632
37.999
F-
208.2511
208.8493
34.179
Cl-
189.9536
190.4610
33.020
Br-
186.8851
187.3791
32.701
I-
183.0301
183.4953
32.596
CN-
190.7953
191.5825
43.356
NC-
190.7953
191.5570
43.236
NCS-
210.7172
211.7441
48.639
SCN-
210.7060
211.7266
47.764
NH2-
182.1513
182.7444
66.401
OH-
193.0291
193.6590
49.627
SH-
181.5719
182.0676
44.651
CH3-
174.8839
175.4047
79.583
CF3-
314.6232
316.0729
53.964
CCl3-
259.5083
260.7973
48.964
C2H5188.1680
188.9320
119.752
Total energies at the restricted Hartree Fock, E(RHF), and Moller-Plesset second order
perturbation theory, E(MP2), levels are reported in hartrees
This is the enthalpic correction (in kcal mol-1), calculated using RHF-determined
vibrational frequencies, which includes the zero point energy and corrects enthalpies from
0 K to 298.15 K.
Methane Activation by Mercury(II) Complexes
Contribution from the Department of Chemistry
University of Memphis
Memphis, TN 38152
by
Thomas R.Cundari and Akihiko Yoshikawa
Tables of Cartesian coordinates (in Å
) are given for all optimized geometries determined in
this study (16 pages). Enthalpic data are also given. Ordering information is given on any current
masthead page.
June 9, 1998
Cartesian Coordinates (in Å) for Optimized Stationary Points
0.000
0.000
0.000
HgH2
0.000
0.000
0.000
0.000
-1.690
1.690
Hg(1)
F(2)
F(3)
0.000
0.000
0.000
HgF2
0.000
0.000
0.000
0.000
-1.954
1.954
Hg(1)
Cl(2)
Cl(3)
0.000
0.000
0.000
HgCl2
0.000
0.000
0.000
0.000
-2.327
2.327
Hg(1)
Br(2)
Br(3)
0.000
0.000
0.000
HgBr2
0.000
0.000
0.000
0.000
-2.454
2.454
Hg(1)
I(2)
I(3)
0.000
0.000
0.000
HgI2
0.000
0.000
0.000
0.000
-2.642
2.642
Hg(1)
C(2)
C(3)
N(4)
N(5)
0.000
0.000
0.000
0.000
0.000
Hg(CN)2
0.000
0.000
0.000
0.000
0.000
0.000
-2.067
2.067
-3.221
3.221
Hg(1)
N(2)
N(3)
C(4)
C(5)
0.000
0.000
0.000
0.000
0.000
Hg(NC)2
0.000
0.000
0.000
0.000
0.000
0.000
-2.004
2.004
-3.176
3.176
0.000
0.000
0.000
Hg(NCS)2
0.000
0.000
0.000
0.000
-1.998
1.998
Hg(1)
H(2)
H(3)
Hg(1)
N(2)
N(3)
C(4)
C(5)
S(6)
S(7)
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
-3.173
3.173
-4.785
4.785
0.000
-2.413
2.413
-2.621
2.621
-2.777
2.777
Hg(SCN)2
0.000
0.000
0.000
1.644
-1.644
2.748
-2.748
-0.352
-0.374
-0.374
0.075
0.075
0.374
0.374
0.000
-2.051
2.051
-2.425
2.425
-2.425
2.425
Hg(NH2)2
0.000
0.000
0.000
-0.491
0.491
-0.491
0.491
0.000
0.000
0.000
0.807
-0.807
-0.807
0.807
Hg(1)
O(2)
O(3)
H(4)
H(5)
0.000
-1.989
1.989
-2.341
2.341
Hg(OH)2
0.000
0.103
-0.103
0.762
-0.762
-0.231
-0.300
-0.300
0.300
0.300
Hg(1)
S(2)
S(3)
H(4)
H(5)
0.000
-2.384
2.384
-2.476
2.476
Hg(SH)2
0.000
0.153
-0.153
1.112
-1.112
-0.443
-0.468
-0.468
0.468
0.468
Hg(1)
C(2)
C(3)
H(4)
H(5)
H(6)
H(7)
H(8)
H(9)
-0.257
-0.257
-0.257
-0.770
-0.770
0.770
-0.770
-0.770
0.770
Hg(CH3)2
0.000
0.000
0.000
0.889
-0.889
0.000
0.889
-0.889
0.000
0.000
-2.153
2.153
2.546
2.546
-2.546
-2.546
-2.546
2.546
Hg(1)
-0.309
Hg(CF3)2
0.000
0.000
Hg(1)
S(2)
S(3)
C(4)
C(5)
N(6)
N(7)
Hg(1)
N(2)
N(3)
H(4)
H(5)
H(6)
H(7)
C(2)
C(3)
F(4)
F(5)
F(6)
F(7)
F(8)
F(9)
Hg(1)
C(2)
C(3)
Cl(4)
Cl(5)
Cl(6)
Cl(7)
Cl(8)
Cl(9)
Hg(1)
C(2)
C(3)
C(4)
C(5)
H(6)
H(7)
H(8)
H(9)
H(10)
H(11)
H(12)
H(13)
H(14)
H(15)
Hg(1)
C(2)
C(3)
C(4)
C(5)
H(6)
H(7)
-0.309
-0.309
-0.928
-0.928
0.928
-0.928
-0.928
0.928
0.000
0.000
1.071
-1.071
0.000
1.071
-1.071
0.000
-2.166
2.166
2.684
2.684
-2.684
-2.684
-2.684
2.684
-0.419
-0.419
-0.419
-1.258
-1.258
1.258
-1.258
-1.258
1.258
Hg(CCl3)2
0.000
0.000
0.000
1.452
-1.452
0.000
1.452
-1.452
0.000
0.000
-2.170
2.170
2.789
2.789
-2.789
-2.789
-2.789
2.789
0.000
-2.162
2.162
-2.741
2.741
-2.534
2.534
-2.534
2.534
-3.843
3.843
-2.419
2.419
-2.419
2.419
cis-Hg(C2H5)2
0.000
0.000
0.000
0.000
0.000
-0.879
-0.879
0.879
0.879
0.000
0.000
-0.886
-0.886
0.886
0.886
-0.779
-0.727
-0.727
0.706
0.706
-1.274
-1.274
-1.274
-1.274
0.698
0.698
1.274
1.274
1.274
1.274
0.000
-2.166
2.166
-2.789
2.789
-2.524
2.524
trans-Hg(C2H5)2
0.000
0.053
-0.053
1.467
-1.467
-0.504
0.504
0.000
0.000
0.000
0.000
0.000
0.878
-0.878
H(8)
H(9)
H(10)
H(11)
H(12)
H(13)
H(14)
H(15)
Hg(1)
C(2)
H(3)
H(4)
H(5)
H(6)
-2.524
2.524
-3.891
3.891
-2.488
2.488
-2.488
2.488
-0.504
0.504
1.420
-1.420
2.047
-2.047
2.047
-2.047
-0.878
0.878
0.000
0.000
0.885
-0.885
-0.885
0.885
0.000
0.000
0.514
0.514
-1.028
0.000
HgMeH
0.000
0.000
-0.890
0.890
0.000
0.000
1.348
-0.803
-1.194
-1.194
-1.194
3.038
Hg(1)
F(2)
C(3)
H(4)
H(5)
H(6)
0.000
0.000
0.000
0.515
0.515
-1.031
HgMeF
0.000
0.000
0.000
-0.893
0.893
0.000
Hg(1)
Cl(2)
C(3)
H(4)
H(5)
H(6)
0.000
0.000
0.000
-0.516
-0.516
1.033
HgMeCl
0.000
0.000
0.000
-0.894
0.894
0.000
1.207
3.576
-0.919
-1.288
-1.288
-1.288
0.000
0.000
0.000
0.516
0.516
-1.033
HgMeBr
0.000
0.000
0.000
0.894
-0.894
0.000
1.193
3.687
-0.943
-1.313
-1.313
-1.312
Hg(1)
I(2)
C(3)
H(4)
H(5)
H(6)
0.000
0.000
0.000
0.516
0.516
-1.033
HgMeI
0.000
0.000
0.000
0.894
-0.894
0.000
1.167
3.844
-0.976
-1.345
-1.345
-1.345
Hg(1)
C(2)
C(3)
H(4)
H(5)
H(6)
N(7)
0.000
0.000
0.000
0.514
0.514
-1.029
0.000
HgMe(CN)
0.000
0.000
0.000
0.891
-0.891
0.000
0.000
0.607
2.721
-1.516
-1.897
-1.897
-1.897
3.878
0.000
0.000
0.000
HgMe(NC)
0.000
0.000
0.000
0.611
2.673
-1.502
Hg(1)
Br(2)
C(3)
H(4)
H(5)
H(6)
Hg(1)
N(2)
C(3)
1.260
3.256
-0.850
-1.222
-1.222
-1.222
H(4)
H(5)
H(6)
C(7)
0.515
0.515
-1.031
0.000
0.893
-0.893
0.000
0.000
-1.875
-1.875
-1.875
3.844
Hg(1)
N(2)
C(3)
H(4)
H(5)
H(6)
C(7)
S(8)
0.000
0.000
0.000
0.516
0.516
-1.032
0.000
0.000
HgMe(NCS)
0.000
0.000
0.000
0.894
-0.894
0.000
0.000
0.000
Hg(1)
S(2)
C(3)
H(4)
H(5)
H(6)
C(7)
N(8)
-0.126
2.331
-2.257
-2.610
-2.610
-2.654
2.518
2.654
HgMe(SCN)
1.143
1.114
1.212
1.738
1.738
0.190
-0.591
-1.738
0.000
0.000
0.000
-0.895
0.895
0.000
0.000
0.000
Hg(1)
N(2)
C(3)
H(4)
H(5)
H(6)
H(7)
H(8)
0.337
0.290
0.266
-0.772
0.772
0.772
0.743
0.743
HgMe(NH2)
-0.023
-2.088
2.105
2.466
2.504
2.504
-2.504
-2.504
0.000
0.000
0.000
0.000
-0.890
0.890
-0.809
0.809
Hg(1)
O(2)
C(3)
H(4)
H(5)
H(6)
H(7)
-0.143
-0.031
-0.148
-0.662
-0.662
0.883
-0.883
HgMe(OH)
0.018
2.038
-2.098
-2.478
-2.478
-2.475
2.478
0.000
0.000
0.000
-0.892
0.892
0.000
0.000
0.200
0.222
0.217
0.220
-0.673
HgMe(SH)
-0.027
2.387
-2.165
-2.546
-2.549
0.257
0.259
0.256
-0.773
0.773
Hg(1)
S(2)
C(3)
H(4)
H(5)
-0.078
1.992
-2.190
-2.559
-2.559
-2.559
3.164
4.790
H(6)
H(7)
1.111
-1.111
-2.536
2.549
0.773
0.259
Hg(1)
C(2)
C(3)
H(4)
H(5)
H(6)
F(7)
F(8)
F(9)
Hg(1)
C(2)
C(3)
H(4)
H(5)
H(6)
Cl(7)
Cl(8)
Cl(9)
Hg(1)
C(2)
C(3)
H(4)
H(5)
H(6)
C(7)
H(8)
H(9)
H(10)
H(11)
H(12)
Hg(1)
H(2)
H(3)
C(4)
H(5)
H(6)
H(7)
H(8)
0.000
0.000
0.000
0.515
0.515
-1.030
0.619
0.619
-1.237
HgMe(CF3)
0.000
0.000
0.000
0.892
-0.892
0.000
1.072
-1.072
0.000
-0.075
2.113
-2.206
-2.589
-2.589
-2.589
2.645
2.645
2.645
0.000
0.000
0.000
0.516
0.516
-1.032
0.839
0.839
-1.678
HgMe(CCl3)
0.000
0.000
0.000
0.893
-0.893
0.000
1.453
-1.453
0.000
-0.118
2.080
-2.245
-2.620
-2.620
-2.620
2.714
2.714
2.714
-0.621
-0.624
-0.631
0.358
-0.900
-1.360
0.773
-1.191
-1.190
1.359
1.360
0.698
HgMe(C2H5)
-0.484
1.556
-2.514
-2.803
-3.215
-2.639
2.179
1.586
2.173
1.614
2.205
3.215
0.074
-0.648
0.794
1.177
-0.011
1.608
-0.868
-1.590
0.066
-1.608
0.062
-1.236
-0.498
1.489
-1.489
-0.283
0.782
0.621
-0.863
-0.863
[HgH2·CH4]_
-0.897
-0.328
-2.218
1.584
0.502
2.218
1.849
1.849
0.000
0.000
0.000
0.000
0.000
0.000
-0.897
0.897
Hg(1)
F(2)
F(3)
C(4)
H(5)
H(6)
H(7)
H(8)
Hg(1)
Cl(2)
Cl(3)
C(4)
H(5)
H(6)
H(7)
H(8)
Hg(1)
Br(2)
Br(3)
C(4)
H(5)
H(6)
H(7)
H(8)
Hg(1)
I(2)
I(3)
C(4)
H(5)
H(6)
H(7)
H(8)
Hg(1)
C(2)
C(3)
C(4)
-0.561
1.673
-1.673
-0.175
0.826
0.642
-0.768
-0.768
[HgF2·CH4]_
-0.732
-0.166
-2.376
1.635
0.772
2.376
1.837
1.837
0.000
0.000
0.000
0.000
0.000
0.000
-0.900
0.900
-0.849
2.034
-2.034
-0.398
0.709
0.492
-0.961
-0.961
[HgCl2·CH4]_
-0.454
-0.043
-2.462
1.813
0.940
2.462
2.074
2.074
0.000
0.000
0.000
0.000
0.000
0.000
-0.904
0.904
-0.892
2.159
-2.159
-0.407
0.502
-0.964
-0.964
0.721
[HgBr2·CH4]_
-0.389
-0.083
-2.488
1.868
2.488
2.143
2.143
0.953
0.000
0.000
0.000
0.000
0.000
-0.904
0.904
0.000
-0.936
2.395
-2.395
-0.304
-1.380
0.124
0.124
0.750
[HgI2·CH4]_
-0.255
-0.121
-2.442
1.993
2.232
2.442
2.442
0.963
0.000
0.000
0.000
0.000
0.000
-0.903
0.903
0.000
-0.379
2.227
-1.607
0.038
[Hg(CN)2·CH4]_
-0.206
0.265
-1.880
2.109
0.000
0.000
0.000
-0.006
H(5)
H(6)
H(7)
H(8)
N(9)
N(10)
1.151
0.905
-0.546
-0.524
-2.316
2.316
1.273
2.791
2.348
2.356
-2.791
-0.900
-0.007
-0.021
-0.903
0.903
-0.002
0.013
Hg(1)
N(2)
N(3)
C(4)
H(5)
H(6)
H(7)
H(8)
C(9)
C(10)
Hg(1)
N(2)
N(3)
C(4)
H(5)
H(6)
H(7)
H(8)
C(9)
C(10)
S(11)
S(12)
-0.853
1.646
-1.804
-0.568
0.513
0.274
-1.147
-1.147
-2.378
2.378
[Hg(NC)2·CH4]_
-0.109
0.552
-1.894
2.203
1.413
2.917
2.420
2.420
-2.917
-0.370
0.000
0.000
0.000
0.000
0.000
0.000
0.905
-0.905
0.000
0.000
-1.293
1.274
-2.387
-0.708
0.279
0.214
-1.252
-1.252
-3.087
2.447
-4.048
4.048
[Hg(NCS)2·CH4]_
0.550
0.860
-1.151
2.786
1.868
3.393
3.077
3.077
-2.095
0.700
-3.393
0.476
0.000
0.000
0.000
0.000
0.000
0.000
0.905
-0.905
0.000
0.000
0.000
0.000
[Hg(SCN)2·CH4]_
Hg(1)
-1.667
0.786
0.000
S(2)
1.677
0.590
0.000
S(3)
-3.230
-1.030
0.000
C(4)
-0.623
2.819
0.000
H(5)
0.187
1.720
0.000
H(6)
0.396
3.242
0.000
H(7)
-1.103
3.200
-0.909
H(8)
-1.103
3.200
0.909
C(9)
-2.118
-2.338
0.000
N(10)
-1.403
-3.242
0.000
C(11)
2.637
1.995
0.000
N(12)
3.230
2.991
0.000
-1
There are two imaginary modes. The second one is 39 cm .
Hg(1)
N(2)
N(3)
C(4)
-0.090
1.851
-1.756
-0.197
[Hg(NH2)2·CH4]_
-0.756
0.255
-1.955
2.062
0.032
-0.062
-0.066
0.306
H(5)
H(6)
H(7)
H(8)
H(9)
H(10)
H(11)
H(12)
1.144
0.246
-0.468
-1.164
2.360
2.525
-1.594
-2.525
1.182
2.855
2.557
1.820
0.254
0.097
-2.855
-1.531
0.100
0.944
-0.649
0.800
-0.944
0.685
0.377
0.446
Hg(1)
O(2)
O(3)
C(4)
H(5)
H(6)
H(7)
H(8)
H(9)
H(10)
Hg(1)
S(2)
S(3)
C(4)
H(5)
H(6)
H(7)
H(8)
H(9)
H(10)
Hg(1)
C(2)
C(3)
C(4)
H(5)
H(6)
H(7)
H(8)
H(9)
H(10)
H(11)
H(12)
H(13)
H(14)
-0.749
1.414
-2.157
-0.410
0.667
0.312
-0.864
-1.186
2.157
-1.796
[Hg(OH)2·CH4]_
-0.485
0.136
-1.929
2.000
1.117
2.793
2.293
2.059
-0.010
-2.793
0.116
-0.184
0.292
0.088
-0.010
0.354
-0.870
0.870
0.409
0.086
-0.713
2.132
-2.211
-0.187
0.885
0.619
-0.377
-1.068
2.211
-1.259
[Hg(SH)2·CH4]_
-0.093
0.100
-1.947
2.231
1.269
2.893
2.470
2.505
0.129
-2.893
-0.169
0.026
-0.146
-0.313
-0.115
0.037
-1.368
0.288
1.368
-0.106
-0.308
2.134
-1.632
-0.232
0.881
0.579
-0.846
-0.846
2.468
2.468
2.674
-2.674
-1.448
-1.448
[Hg(CH3)2·CH4]_
-0.497
0.172
-2.172
2.033
1.013
2.783
2.230
2.230
-0.380
-0.380
1.135
-1.834
-2.783
-2.783
0.000
0.000
0.000
0.000
0.000
0.000
-0.894
0.894
-0.895
0.895
0.000
0.000
-0.892
0.892
Hg(1)
C(2)
C(3)
C(4)
H(5)
H(6)
H(7)
H(8)
F(9)
F(10)
F(11)
F(12)
F(13)
F(14)
Hg(1)
C(2)
C(3)
C(4)
H(5)
H(6)
H(7)
H(8)
Cl(9)
Cl(10)
Cl(11)
Cl(12)
Cl(13)
Cl(14)
Hg(1)
C(2)
C(3)
C(4)
H(5)
H(6)
H(7)
H(8)
H(9)
H(10)
C(11)
C(12)
-0.661
2.112
-1.676
-0.265
0.682
0.609
-0.844
-0.844
2.464
2.464
3.004
-3.004
-1.373
-1.373
[Hg(CF3)2·CH4]_
-0.198
0.319
-2.097
2.157
1.224
2.828
2.388
2.388
-0.440
-0.440
1.343
-1.948
-2.828
-2.828
0.000
0.000
0.000
0.000
0.000
0.000
-0.903
0.903
-1.077
1.077
0.000
0.000
-1.071
1.071
-0.797
2.100
-2.014
-0.465
0.597
-1.522
-0.458
-0.108
1.926
1.836
3.746
-3.746
-1.743
-1.602
[Hg(CCl3)2·CH4]_
-0.136
0.929
-1.952
2.306
1.634
2.126
2.760
3.020
-0.156
-0.197
1.564
-1.515
-2.825
-3.020
0.103
0.032
0.040
0.043
0.052
0.315
-0.955
0.797
-1.437
1.489
0.097
0.154
-1.489
1.403
-0.439
2.067
-1.723
-0.325
0.754
0.508
-0.932
-0.932
2.433
2.433
2.720
-3.231
[Hg(C2H5)2·CH4]_
-0.458
0.268
-2.180
2.068
1.015
2.792
2.279
2.279
0.823
0.823
-1.139
-1.861
0.000
0.000
0.000
0.000
0.000
0.000
-0.895
0.895
-0.882
0.882
0.000
0.000
H(13)
H(14)
H(15)
H(16)
H(17)
H(18)
H(19)
H(20)
-1.455
-1.455
-3.525
-3.525
-3.822
3.822
2.432
2.432
0.000
0.000
-2.776
-2.776
-1.283
-1.283
-2.792
-1.076
-1.725
-1.725
H2
0.000
0.000
H(1)
H(2)
0.374
-0.374
H(1)
F(2)
0.000
0.000
HF
0.000
0.000
-0.459
0.459
H(1)
Cl(2)
0.000
0.000
HCl
0.000
0.000
-0.639
0.639
0.000
0.000
HBr
0.000
0.000
-0.713
0.713
0.000
0.000
HI
0.000
0.000
-0.807
0.807
0.000
0.000
0.000
HCN
0.000
0.000
0.000
-1.113
-0.035
1.113
H(1)
N(2)
C(3)
0.000
0.000
0.000
HNC
0.000
0.000
0.000
-1.084
-0.083
1.084
H(1)
N(2)
C(3)
S(4)
-1.351
-0.345
0.336
1.351
HNCS
1.143
1.064
0.077
-1.143
0.000
0.000
0.000
0.000
H(1)
Br(2)
H(1)
I(2)
H(1)
C(2)
N(3)
HSCN
-0.881
0.881
-0.887
0.887
0.000
0.000
-0.886
0.886
H(1)
S(2)
C(3)
N(4)
N(1)
H(2)
H(3)
H(4)
O(1)
H(2)
H(3)
-1.070
0.247
0.714
1.070
-1.129
-1.375
0.279
1.375
0.000
0.000
0.000
0.000
-0.234
-0.700
-0.700
0.700
NH3
0.000
0.810
-0.810
0.000
0.200
-0.200
-0.200
-0.200
0.000
-0.756
0.756
H2O
0.000
0.000
0.000
-0.295
0.295
0.295
0.000
-0.982
0.982
H2S
0.000
0.000
0.000
-0.456
0.456
0.456
C(1)
H(2)
H(3)
H(4)
H(5)
0.000
0.634
-0.634
-0.634
0.634
CH4
0.000
-0.634
0.634
-0.634
0.634
0.000
-0.634
-0.634
0.634
0.634
C(1)
F(2)
F(3)
F(4)
H(5)
-0.310
-0.930
-0.930
0.930
-0.310
CHF3
0.000
1.074
-1.074
0.000
0.000
-0.314
-0.778
-0.778
-0.778
0.778
C(1)
Cl(2)
Cl(3)
Cl(4)
H(5)
-0.421
-1.263
-1.263
1.263
-0.421
CHCl3
0.000
1.458
-1.458
0.000
0.000
-0.276
-0.810
-0.810
-0.810
0.810
0.000
0.000
-0.888
0.888
0.000
0.888
-0.888
0.000
C2H6
0.000
0.000
-0.513
-0.513
-1.026
0.513
0.513
1.026
-0.769
0.769
-1.164
-1.164
1.164
1.164
1.164
-1.164
S(1)
H(2)
H(3)
C(1)
C(2)
H(3)
H(4)
H(5)
H(6)
H(7)
H(8)
Table S-2
Calculated Energetic Data for Reactants LsHgLaa
a.
b.
c.
La, Ls
-E(RHF)b
-E(MP2)b
H(298.15)c
H-
153.9363
154.0578
9.889
F-
200.5298
200.9831
5.246
Cl-
182.2664
182.6250
4.756
Br-
179.2043
179.5463
4.591
I-
175.3586
175.6719
4.533
CN-
183.1260
183.7646
14.931
NC-
183.0994
183.7182
14.307
NCS-
203.0209
203.8999
20.029
SCN-
203.0314
203.9039
19.570
NH2-
174.4438
174.8946
37.009
OH-
185.3198
185.8048
20.617
SH-
173.8965
174.2414
16.121
CH3-
167.2300
167.6005
50.302
CF3-
306.9647
308.2660
24.278
CCl3-
251.8310
252.9790
19.704
C2H5-
180.5159
181.1287
90.957
Pertinent calculated data for methane reactant are: E(RHF) = -7.8034 hartrees, E(MP2) =
-7.9278 hartrees, H(298.15K) = 31.911 kcal mol-1.
Total energies at the restricted Hartree Fock, E(RHF), and Moller-Plesset second order
perturbation theory, E(MP2), levels are reported in hartrees
This is the enthalpic correction (kcal mol-1), calculated using RHF-determined vibrational
frequencies, which includes the zero point energy and corrects enthalpies from 0 K to
298.15 K.
Table S-3
Calculated Energetic Data for Products LsHgCH3a
a.
b.
c.
Ls
-E(RHF)b
-E(MP2)b
H(298.15)c
H-
160.5833
160.8292
30.248
F-
183.8943
184.3059
28.294
Cl-
174.7596
175.1227
28.154
Br-
173.2255
173.5819
27.898
I-
171.3004
171.6424
27.827
CN-
175.1857
175.6893
33.006
NC-
175.1770
175.6720
32.931
NCS-
185.1412
185.7637
35.735
SCN-
185.1406
185.7615
35.588
NH2-
170.8393
171.2501
44.025
OH-
176.2817
176.7094
35.941
SH-
170.5667
170.9241
33.735
CH3-
167.2300
167.6005
50.302
CF3-
237.1016
237.9376
37.980
CCl3-
209.5363
210.2936
35.490
C2H5173.8729
174.3646
70.984
Pertinent calculated data for HLa products are given in Table S-4.
Total energies at the restricted Hartree Fock, E(RHF), and Moller-Plesset second order
perturbation theory, E(MP2), levels are reported in hartrees
This is the enthalpic correction (in kcal mol-1), calculated using RHF-determined
vibrational frequencies, which includes the zero point energy and corrects enthalpies from
0 K to 298.15 K.
Table S-4
Calculated Energetic Data for Products HLa
a
b.
La
-E(RHF)a
-E(MP2)a
H(298.15)b
H
1.1246
1.1405
8.583
F
24.4356
24.6033
8.339
Cl
15.2657
15.3937
6.652
Br
13.7232
13.8429
6.091
I
11.7917
11.8967
5.59
CN
15.7181
15.9828
13.391
NC
15.7025
15.9569
13.174
NCS
25.6597
26.0468
14.893
SCN
25.6564
26.0351
14.468
NH2
11.4099
11.5719
25.148
OH
16.8434
17.0223
16.555
SH
11.0920
11.2075
12.619
CH3
7.8034
7.9278
31.911
CF3
77.6781
78.2643
20.075
CCl3
50.1061
50.6100
16.968
C2H5
14.4519
14.6942
51.992
Total energies at the restricted Hartree Fock, E(RHF), and Moller-Plesset second order
perturbation theory, E(MP2), levels are reported in hartrees
This is the enthalpic correction (in kcal mol-1), calculated using RHF-determined
vibrational frequencies, which includes the zero point energy and corrects enthalpies from
0 K to 298.15 K.
Table S-5
Thermodynamic data for [LsHgLa·HtCH3]_
a.
b.
La,s
-E(RHF)a
-E(MP2)a
H(298.15)b
H-
161.5922
161.8632
37.999
F-
208.2511
208.8493
34.179
Cl-
189.9536
190.4610
33.020
Br-
186.8851
187.3791
32.701
I-
183.0301
183.4953
32.596
CN-
190.7953
191.5825
43.356
NC-
190.7953
191.5570
43.236
NCS-
210.7172
211.7441
48.639
SCN-
210.7060
211.7266
47.764
NH2-
182.1513
182.7444
66.401
OH-
193.0291
193.6590
49.627
SH-
181.5719
182.0676
44.651
CH3-
174.8839
175.4047
79.583
CF3-
314.6232
316.0729
53.964
CCl3-
259.5083
260.7973
48.964
C2H5188.1680
188.9320
119.752
Total energies at the restricted Hartree Fock, E(RHF), and Moller-Plesset second order
perturbation theory, E(MP2), levels are reported in hartrees
This is the enthalpic correction (in kcal mol-1), calculated using RHF-determined
vibrational frequencies, which includes the zero point energy and corrects enthalpies from
0 K to 298.15 K.