suppmat_649.doc 56KB Jun 05 2011 09:30:57 PM

Electronic Supplementary Information
Intramolecular C-H····Ccarbene Hydrogen Bonds And Competing Interactions In
Mono-Protonated Tripodal Carbenes

Siân T. Howard
a

Colin D. Abernethy

Department Of Chemistry,

b

Department of Pure and Applied Chemistry

Cardiff University,

University of Strathclyde,

Cardiff CF10 3TB,


Glasgow G1 1XL

Wales, U. K.

Scotland, U. K.

Table 1s

Results For Compounds Needed To Calculate
Resonance Energies And Hydrogen-Bond Strengths
B3LYP/6-31+G**

Compound

HF/3-21G Thermal

r(X-N)/Å

Energy (a.u.)


(C3N2H3)-CH3

1.455

-265.50739

293.1

[(C3N2H4)-CH3]+

1.473

-265.92860

333.3

(C3N2H3)-SiH3

1.779


-516.90547

257.1

[(C3N2H3)-SiH3]+

1.851

-517.32661

297.0

(C3N2H3)-PH2

1.767

-568.13694

235.8


[(C3N2H3)-PH3]+

1.828

-568.55549

275.6

C3N2H4

-

C3N2H5+

-

(C3N2H4)2

-226.19421
-226.60810

-

-452.83505

Energy (kJ/mol)

211.6
251.7
473.0

CH4

-

-40.52614

133.5

SiH4


-

-291.88987

92.6

PH3

-

-343.14691

72.4

Table 2s B3LYP/6-31+G** Cartesian Coordinates (Å)
and NPA atomic charges (Q, in electrons) of 1
Atomic number
1
5
7

7
7
6
6
6
7
7
7
6
6
6
6
6
6
1
1
1
1
1
1

1
1
1

x
0.000000
0.000000
-0.193644
-1.168255
1.361899
0.431487
-2.431583
2.000096
0.000000
-3.096650
3.096650
-0.977261
-1.073486
2.050747
-0.865099

-2.292683
3.157782
-1.566510
-0.149542
1.716052
-1.323835
-2.632551
3.956386
0.278965
-4.063542
3.784577

y
0.000000
0.000000
1.460785
-0.898093
-0.562692
2.558631
-0.905637

-1.652994
3.575703
-1.787852
-1.787852
1.803777
-1.748221
-0.055556
3.146827
-2.322611
-0.824216
1.077101
-1.895188
0.818087
3.804125
-3.048537
-0.755588
4.531114
-2.023966
-2.507148


z
-2.160345
-0.964516
-0.416872
-0.416872
-0.416872
-0.951621
-0.951621
-0.951621
-0.130265
-0.130265
-0.130265
0.680626
0.680626
0.680626
0.874714
0.874714
0.874714
1.217885
1.217885
1.217885
1.598895
1.598895
1.598895
-0.281494
-0.281494
-0.281494

Q
-0.02432
0.69486
-0.64442
-0.64442
-0.64442
0.09363
0.09363
0.09363
-0.64873
-0.64873
-0.64873
-0.09002
-0.09002
-0.09002
-0.17004
-0.17004
-0.17004
0.24591
0.24591
0.24591
0.22460
0.22460
0.22460
0.43224
0.43224
0.43224

Table 3s B3LYP/6-31+G** Cartesian Coordinates (Å)
and NPA atomic charges (Q, in electrons) of 2
Atomic number
1
6
7
7
7
6
6
6
7
7
7
6
6
6
6
6
6
1
1
1
1
1
1
1
1
1

x
0.000000
0.000000
-0.181812
-1.101779
1.283591
0.379218
-2.286800
1.907582
0.000000
-3.014091
3.014091
-0.881198
-1.101446
1.982644
-0.763867
-2.329871
3.093738
-1.414399
-0.243791
1.658190
-1.163649
-2.750884
3.914533
0.240561
-3.953974
3.713413

y
0.000000
0.000000
1.377194
-0.846051
-0.531143
2.421627
-0.882401
-1.539226
3.480372
-1.740186
-1.740186
1.780600
-1.653440
-0.127160
3.131322
-2.227189
-0.904133
1.098109
-1.773960
0.675851
3.848280
-2.931890
-0.916390
4.426768
-2.005052
-2.421716

z
-1.869520
-0.782205
-0.334241
-0.334241
-0.334241
-1.026861
-1.026861
-1.026861
-0.255979
-0.255979
-0.255979
0.808589
0.808589
0.808589
0.855150
0.855150
0.855150
1.450153
1.450153
1.450153
1.555278
1.555278
1.555278
-0.507593
-0.507593
-0.507593

Q
0.31919
0.35337
-0.48553
-0.48553
-0.48553
0.13403
0.13403
0.13403
-0.62447
-0.62447
-0.62447
-0.10649
-0.10649
-0.10649
-0.10973
-0.10973
-0.10973
0.26079
0.26079
0.26079
0.25157
0.25157
0.25157
0.45563
0.45563
0.45563

Table 4s B3LYP/6-31+G** Cartesian Coordinates (Å)
and NPA atomic charges (Q, in electrons) of 3
Atomic number
1
14
7
7
7
6
6
6
7
7
7
6
6
6
6
6
6
1
1
1
1
1
1
1
1
1

x
0.000000
0.000000
0.486779
1.125615
-1.612394
-0.329103
2.462430
-2.133327
0.341844
3.028786
-3.370630
1.624793
0.902070
-2.526863
1.529231
2.112150
-3.641381
2.397311
-0.084470
-2.312841
2.189233
2.390807
-4.580040
0.000000
4.019990
-4.019990

y
0.000000
0.000000
1.580790
-1.211958
-0.368832
2.653361
-1.041669
-1.611692
3.694705
-2.143398
-1.551307
1.979695
-2.396960
0.417265
3.321803
-2.985254
-0.336549
1.286551
-2.719408
1.432857
4.024620
-3.908241
-0.116379
4.641885
-2.320942
-2.320942

z
2.300228
0.836919
0.206625
0.206625
0.206625
0.524314
0.524314
0.524314
-0.035045
-0.035045
-0.035045
-0.513435
-0.513435
-0.513435
-0.668080
-0.668080
-0.668080
-0.803365
-0.803365
-0.803365
-1.152189
-1.152189
-1.152189
0.025342
0.025342
0.025342

Q
-0.18112
2.00797
-0.86680
-0.86680
-0.86680
0.10822
0.10822
0.10822
-0.62231
-0.62231
-0.62231
-0.07656
-0.07656
-0.07656
-0.12204
-0.12204
-0.12204
0.26487
0.26487
0.26487
0.25161
0.25161
0.25161
0.45406
0.45406
0.45406

Table 5s B3LYP/6-31+G** Cartesian Coordinates (Å)
and NPA atomic charges (Q, in electrons) of 4
Atomic number
15
7
7
7
6
6
6
7
7
7
6
6
6
6
6
6
1
1
1
1
1
1
1
1
1

x
0.000000
0.228000
1.204969
-1.432969
-0.354986
2.465172
-2.110186
0.000000
3.124575
-3.124575
0.926486
1.104999
-2.031485
0.780025
2.331697
-3.111722
1.470658
0.189739
-1.660397
1.167723
2.691281
-3.859004
-0.264496
4.091969
-3.827473

y
0.000000
1.523014
-0.958961
-0.564053
2.641584
-1.013365
-1.628219
3.607948
-1.803974
-1.803974
1.810850
-1.707785
-0.103065
3.142760
-2.246901
-0.895859
1.068177
-1.807716
0.739539
3.781809
-2.902182
-0.879627
4.572292
-2.057086
-2.515206

z
1.221434
0.353788
0.353788
0.353788
0.914761
0.914761
0.914761
0.024014
0.024014
0.024014
-0.830590
-0.830590
-0.830590
-1.034848
-1.034848
-1.034848
-1.390900
-1.390900
-1.390900
-1.813274
-1.813274
-1.813274
0.156454
0.156454
0.156454

Q
1.55256
-0.78332
-0.78332
-0.78332
0.13805
0.13805
0.13805
-0.62649
-0.62649
-0.62649
-0.10542
-0.10542
-0.10542
-0.11035
-0.11035
-0.11035
0.26098
0.26098
0.26098
0.25279
0.25279
0.25279
0.45625
0.45625
0.45625

Table 6s B3LYP/6-31+G** Cartesian Coordinates (Å)
and NPA atomic charges (Q, in electrons) of 1H
Atomic number
1
5
7
7
7
6
6
6
7
7
7
6
6
6
6
6
6
1
1
1
1
1
1
1
1
1
1

x
0.028238
-0.027872
1.075489
-1.419149
0.340633
2.384853
-1.772750
1.508805
3.036911
-3.117516
1.374887
0.884415
-2.519467
-0.472137
2.106502
-3.604006
0.174258
-0.105132
-2.435394
-1.424036
2.388003
-4.639299
-0.107064
4.041070
-3.682039
2.082159
2.811214

y
-0.019270
0.021197
-1.024660
-0.434133
1.433909
-0.794702
-0.790818
2.070044
-1.909401
-1.018910
3.292781
-2.329818
-0.446402
2.254628
-2.895574
-0.815438
3.439746
-2.733095
-0.189492
1.926833
-3.876472
-0.947628
4.339306
-1.993314
-1.308759
4.008059
0.160749

z
1.960456
0.755972
0.221766
0.298737
0.238814
0.251774
-0.983271
0.586628
-0.135478
-0.860611
-0.010645
-0.189623
1.158220
-0.540424
-0.418949
0.428771
-0.698423
-0.322748
2.203582
-0.926407
-0.767616
0.705961
-1.225333
-0.208903
-1.645408
0.068403
0.541854

Q
-0.03551
0.68977
-0.49062
-0.66708
-0.64755
0.24579
0.07410
0.05665
-0.55709
-0.63139
-0.62352
-0.03467
-0.08545
-0.07783
-0.10832
-0.13707
-0.14072
0.27614
0.25141
0.25426
0.25888
0.24473
0.24265
0.46455
0.44758
0.44570
0.28460

Table 7s B3LYP/6-31+G** Cartesian Coordinates (Å)
and NPA atomic charges (Q, in electrons) of 2H+
Atomic number
1
6
7
7
7
6
6
6
7
7
7
6
6
6
6
6
6
1
1
1
1
1
1
1
1
1
1

x
0.033249
0.003685
-0.156926
-1.137996
1.270247
0.648632
-1.690723
2.358281
0.150090
-2.625495
3.318595
-1.199091
-1.708067
1.561412
-1.005411
-2.665420
2.876433
-1.986231
-1.386751
0.822538
-1.578071
-3.356088
3.512442
0.566421
-3.236262
4.260570
1.540193

y
-0.079746
-0.076285
1.350624
-0.819457
-0.591150
2.025177
-0.632199
-0.550652
3.259170
-1.615056
-1.096225
2.174779
-1.889824
-1.149768
3.380829
-2.390597
-1.472337
1.832397
-2.189505
-1.275863
4.293660
-3.206833
-1.941000
3.986163
-1.752049
-1.238145
1.640843

z
Q
-1.836381 0.30763
-0.745211 0.35276
-0.329868 -0.35495
-0.273703 -0.49514
-0.301974 -0.50943
0.491866 0.28393
0.975198 0.09805
-1.152665 0.13388
0.628239 -0.52649
0.991341 -0.60737
-0.365221 -0.61503
-0.723994 -0.03257
-0.982873 -0.09833
0.957350 -0.11814
-0.122581 -0.05055
-0.165901 -0.07952
0.902694 -0.08190
-1.376963 0.28895
-1.968763 0.26961
1.733234 0.27795
-0.162891 0.28935
-0.310609 0.27252
1.638000 0.27156
1.197546 0.49056
1.784775 0.47038
-0.703094 0.47180
0.960164 0.29049

Table 8s B3LYP/6-31+G** Cartesian Coordinates (Å)
and NPA atomic charges (Q, in electrons) of 3H+
Atomic number
1
14
7
7
7
6
6
6
7
7
7
6
6
6
6
6
6
1
1
1
1
1
1
1
1
1
1

x
-0.035877
0.041739
-0.557284
1.702024
-1.000158
-1.824871
1.995098
-2.319144
-1.890011
3.333615
-2.916347
0.196852
2.857350
-0.816607
-0.635754
3.885445
-2.037524
1.244594
2.840677
0.136537
-0.452546
4.937003
-2.352849
-2.736158
3.869207
-3.903512
-2.639360

y
-0.055146
-0.132681
1.487115
-0.283630
-1.343116
1.920440
-0.285136
-1.180535
3.161881
-0.485978
-2.257433
2.505660
-0.485316
-2.498198
3.554948
-0.612993
-3.074741
2.379945
-0.523574
-2.778287
4.519859
-0.780338
-3.972786
3.716588
-0.541626
-2.444997
1.321248

z
2.285171
0.825331
0.196128
0.332645
0.142151
0.299640
-1.029759
0.537446
-0.191241
-1.021888
-0.020434
-0.385552
1.123620
-0.638604
-0.628901
0.254697
-0.735054
-0.602670
2.201987
-1.057108
-1.074036
0.429010
-1.242823
-0.237912
-1.877435
0.086808
0.687642

Q
-0.16737
1.98337
-0.70914
-0.90142
-0.87613
0.26796
0.11882
0.09430
-0.52965
-0.61037
-0.60057
-0.03577
-0.09631
-0.0755
-0.06875
-0.08705
-0.09029
0.28793
0.26704
0.27230
0.28629
0.27274
0.27156
0.48797
0.47067
0.46911
0.29837

Table 9s B3LYP/6-31+G** Cartesian Coordinates (Å)
and NPA atomic charges (Q, in electrons) of 4H+
Atomic number
15
7
7
7
6
6
6
7
7
7
6
6
6
6
6
6
1
1
1
1
1
1
1
1
1
1

x
-0.081476
0.698438
0.722300
-1.636728
1.834134
1.595054
-1.911071
2.309996
2.112636
-3.261217
0.512018
0.695321
-2.818070
1.537260
1.564339
-3.842461
-0.310319
0.034943
-2.812263
1.772583
1.832778
-4.908672
3.137968
2.796989
-3.788996
1.850013

y
-0.117097
-1.395406
1.318364
-0.030790
-1.823116
2.081322
0.013065
-2.768544
2.977935
0.061453
-2.071937
1.746055
-0.004880
-2.950553
2.790399
0.049767
-1.858409
1.273874
-0.037419
-3.683646
3.407323
0.078119
-3.305502
3.681069
0.101641
1.977587

z
-1.099406
-0.267592
-0.237784
-0.337079
-0.953747
-0.910100
1.027838
-0.115283
-0.063750
1.029422
0.957946
1.088221
-1.118582
1.035337
1.195110
-0.239755
1.620926
1.801730
-2.197228
1.791691
2.038133
-0.401335
-0.333404
-0.315061
1.890914
-1.954419

Q
1.50526
-0.79770
-0.62129
-0.79251
0.14458
0.26108
0.10306
-0.61199
-0.53153
-0.59984
-0.09574
-0.04051
-0.09279
-0.07976
-0.06510
-0.08547
0.27879
0.30160
0.27178
0.27128
0.28631
0.27466
0.47121
0.48817
0.47156
0.28489

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