Supporting Information
Silver Complexes of 1,2,4-triazole Derived N-heterocyclic Carbenes: Synthesis, Structure and Reactivity Studies
Chandrakanta Dasha, Mobin M. Shaikhb and Prasenjit Ghosha*
aDepartment of Chemistry and
bNational Single Crystal X-ray Diffraction Facility,
Indian Institute of Technology Bombay,
Powai, Mumbai 400 076.
Email:
Fax: +91-22-2572-3480
11
Figure S1. Orbital interaction diagram showing the major contributions of the NHC-silver bond in 1b’.
Figure S2. Orbital interaction diagram showing the major contributions of the NHC-silver bond in 2b’.
11
The density functional theory calculations were performed on 1b’ and 2b’ using GAUSSIAN 03[1] suite of quantum chemical programs.
Table S1. B3LYP/SDD, 6-31G* optimized coordinates of 1b’.
E = - 1519.1337532 hartree/particle.
Ag / -0.0001 / -7E-06 / -0.5269O / -2.9404 / -0.1571 / 0.45959
O / 2.94047 / 0.15714 / 0.4597
N / -0.2441 / 3.07638 / 0.02587
N / -1.1041 / 4.14386 / 0.08099
N / -2.0751 / 2.34541 / -0.7536
N / -5.0507 / 0.51728 / -0.1367
H / -5.5624 / 1.15167 / -0.7354
N / 0.24416 / -3.0764 / 0.02587
N / 1.10422 / -4.1438 / 0.081
N / 2.07504 / -2.3452 / -0.7537
N / 5.05071 / -0.5173 / -0.1367
H / 5.56228 / -1.1516 / -0.7356
C / -0.791 / 1.95744 / -0.4764
C / -2.2161 / 3.66618 / -0.3957
H / -3.1306 / 4.23098 / -0.5063
C / 1.14076 / 3.2726 / 0.47965
H / 1.59685 / 2.28189 / 0.53258
H / 1.08541 / 3.68584 / 1.49083
C / 1.91676 / 4.20191 / -0.4513
H / 1.98917 / 3.77812 / -1.4589
H / 2.93086 / 4.34055 / -0.063
H / 1.43671 / 5.18242 / -0.5162
C / -3.1324 / 1.49293 / -1.2865
H / -2.7084 / 0.88312 / -2.0893
H / -3.8943 / 2.14322 / -1.7246
C / -3.7037 / 0.53443 / -0.214
C / -5.8797 / -0.3441 / 0.75928
C / -7.3424 / 0.01441 / 0.45498
H / -7.5456 / 1.07194 / 0.66326
H / -8.0102 / -0.5812 / 1.08379
H / -7.5962 / -0.194 / -0.5916
C / -5.5491 / -0.0303 / 2.22896
H / -4.5013 / -0.247 / 2.4493
H / -6.1762 / -0.6409 / 2.88724
H / -5.7449 / 1.02366 / 2.45505
C / -5.6213 / -1.8265 / 0.43864
H / -5.8552 / -2.0454 / -0.6091
H / -6.2574 / -2.4571 / 1.06875
H / -4.5782 / -2.0896 / 0.62912
C / 0.79089 / -1.9574 / -0.4764
C / 2.21618 / -3.666 / -0.3957
H / 3.13073 / -4.2307 / -0.5063
C / -1.1407 / -3.2727 / 0.47961
H / -1.5969 / -2.2821 / 0.53271
H / -1.0853 / -3.6862 / 1.49072
C / -1.9167 / -4.2019 / -0.4515
H / -1.9891 / -3.778 / -1.459
H / -2.9308 / -4.3407 / -0.0632
H / -1.4365 / -5.1824 / -0.5165
C / 3.13219 / -1.4926 / -1.2866
H / 2.70807 / -0.8827 / -2.0892
H / 3.89404 / -2.1428 / -1.7249
C / 3.70367 / -0.5343 / -0.214
C / 5.87977 / 0.344 / 0.75923
C / 5.54923 / 0.03005 / 2.2289
H / 4.50148 / 0.24691 / 2.44929
H / 6.17636 / 0.6405 / 2.88721
H / 5.74488 / -1.0239 / 2.45489
C / 7.34242 / -0.0147 / 0.45485
H / 7.54559 / -1.0722 / 0.66303
H / 8.01029 / 0.5808 / 1.08369
H / 7.5962 / 0.19382 / -0.5917
C / 5.62152 / 1.82645 / 0.43874
H / 5.85545 / 2.04535 / -0.609
H / 6.25762 / 2.45687 / 1.0689
H / 4.57839 / 2.08959 / 0.62923
Table S2. B3LYP/SDD, 6-31G* optimized coordinates of 2b’.
E = - 1597.7661529 hartree/particle.
Ag / 0.00016 / 2.5E-05 / -0.5732O / 3.00793 / 0.06653 / 0.30833
O / -3.0079 / -0.0664 / 0.30869
N / 0.19691 / -3.0708 / 0.01753
N / 1.03279 / -4.1577 / 0.04751
N / 2.0076 / -2.3973 / -0.859
N / 5.06389 / -0.6406 / -0.4248
H / 5.5251 / -1.2792 / -1.0591
N / -0.197 / 3.0709 / 0.01736
N / -1.033 / 4.15775 / 0.04708
N / -2.0076 / 2.39703 / -0.8592
N / -5.0638 / 0.64051 / -0.4248
H / -5.525 / 1.27853 / -1.0597
C / 0.74835 / -1.9733 / -0.5244
C / 2.13193 / -3.7161 / -0.4899
H / 3.02353 / -4.3075 / -0.6412
C / -1.1706 / -3.207 / 0.57422
H / -1.6311 / -2.2283 / 0.4129
C / -1.9428 / -4.2775 / -0.2017
H / -1.9852 / -4.0393 / -1.2699
H / -2.9679 / -4.3321 / 0.17818
H / -1.4782 / -5.2606 / -0.0814
C / -1.0918 / -3.4957 / 2.0758
H / -0.5919 / -4.4506 / 2.26454
H / -2.1037 / -3.5475 / 2.48946
H / -0.5477 / -2.704 / 2.60151
C / 3.05893 / -1.5786 / -1.452
H / 2.61077 / -0.9586 / -2.2336
H / 3.7773 / -2.252 / -1.9273
C / 3.71413 / -0.6346 / -0.4152
C / 5.96201 / 0.20725 / 0.41497
C / 5.7126 / 1.69311 / 0.10302
H / 5.89389 / 1.90492 / -0.9565
H / 6.39196 / 2.3148 / 0.69567
H / 4.68546 / 1.9746 / 0.34697
C / 5.71458 / -0.0947 / 1.90351
H / 4.68639 / 0.14326 / 2.18544
H / 6.39218 / 0.50512 / 2.52029
H / 5.90242 / -1.1517 / 2.122
C / 7.39669 / -0.1808 / 0.02583
H / 7.59235 / -1.2407 / 0.229
H / 8.11205 / 0.4059 / 0.60902
H / 7.59068 / 0.01658 / -1.0355
C / -0.7483 / 1.97328 / -0.5244
C / -2.1321 / 3.71589 / -0.4904
H / -3.0237 / 4.30721 / -0.6418
C / 1.17038 / 3.20728 / 0.57434
H / 1.63111 / 2.2287 / 0.41289
C / 1.09116 / 3.49563 / 2.07596
H / 0.59097 / 4.45038 / 2.26477
H / 2.103 / 3.54773 / 2.48985
H / 0.54724 / 2.70366 / 2.60141
C / 1.94248 / 4.27805 / -0.2012
H / 1.98516 / 4.04012 / -1.2694
H / 2.96751 / 4.33286 / 0.17894
H / 1.47758 / 5.2611 / -0.0808
C / -3.0587 / 1.57814 / -1.4522
H / -2.6103 / 0.95798 / -2.2335
H / -3.7771 / 2.25134 / -1.9279
C / -3.714 / 0.63444 / -0.4151
C / -5.9619 / -0.2073 / 0.415
C / -5.7144 / 0.09465 / 1.90353
H / -4.6862 / -0.1437 / 2.18542
H / -6.3922 / -0.5049 / 2.52032
H / -5.9018 / 1.15169 / 2.122
C / -7.3966 / 0.18095 / 0.02599
H / -7.5921 / 1.24086 / 0.22927
H / -8.112 / -0.4057 / 0.60914
H / -7.5907 / -0.0163 / -1.0354
C / -5.7127 / -1.6932 / 0.10296
H / -5.8942 / -1.9049 / -0.9565
H / -6.3921 / -2.3148 / 0.69569
H / -4.6856 / -1.9748 / 0.34673
11
Table S3. Natural charge analyses of 1b’ and 2b’.
specie/compound / Ccarbene / Ag / specie/compound / Ccarbene / AuAg+ / 1.00 / Ag+ / 1.00
/ 0.156
0.156 / / 0.155
0.155
1b’ / 0.075
0.075 / 0.526 /
2b’ / 0.076
0.076 / 0.522
Table S4. Mulliken charge analyses of 1b’ and 2b’.
Ag+ / 1.00 / Ag+ / 1.00
/ 0.115
0.115 / / 0.111
0.111
1b’ / 0.339
0.339 / -0.140 /
2b’ / 0.334
0.334 / -0.151
11
Table S5. Electronic configuration of 1b’ and 2b’.
specie/compound / 5s / 4d / 5p / 6pAg+ / 10
1b’ / 0.66 / 9.79 / 0.01
2b’ / 0.67 / 9.79 / 0.01 / 0.01
Table S6. Hybrid orbitals of the Ccarbene-Ag bond in 1b’ and 2b’.
Ccarbene-Ag bond / Ccarbene / Ag
s (%) / p (%) / s (%) / d (%)
1b’ / [C(sp1.54)-Ag(sd0.10)] / 39.33 / 60.66 / 90.50 / 8.95
2b’ / [C(sp1.56)-Ag(sd0.10)] / 39.07 / 60.93 / 90.41 / 9.07
11
Table S7. Charge decomposition analysis (CDA) results showing the donation (d), the donation (b), d/b ratio and the NHC«Ag repulsive polarization (r) for 1b’ and 2b’.
compound /(d) /
(b) / d/b ratio / repulsive polarization (r)
1b’ / 0.667 / 0.054 / 12.35 / -0.060
2b’ / 0.675 / 0.054 / 12.5 / -0.060
Table S8. Bond distance and bond energy of Ccarbene-Ag bond in 1b’ and 2b’.
(Å) / De (Ccarbene-Ag) (kcal/mol)
1b’ / 2.11
2.11 / 88.2
2b’ / 2.11
2.11 / 88.6
References
14
[1][]. GAUSSIAN 03: Gaussian 03, Revision C.02, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A. Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; and Pople, J. A. Gaussian, Inc., Wallingford, CT, 2004.