Table 3. Interactions of Cl– and Water Ligands with the Rest of the Complex in the Gas Phase Optimized X-R and X-P Structures (X = H, NH2, NO2), Respectively: Pt–Cl, Pt–Ow Bond Lengths (in Å); the Total NPA Charges of the Cl– and Water Ligands (q(Cl), q(w)); and ETS-NOCV Energy Decomposition Terms ΔEPauli, ΔEelst, ΔEorb, ΔEdisp, ΔEorbσ, and ΔEorb Obtained at the BLYP-D3BJ/TZ2P//B3LYP/BS1 Levela,b.
| X-R | Pt–Cl | q(Cl) | ΔEPauli | ΔEelst | ΔEorb | ΔEdisp | ΔEorbσ | ΔEorbπ | ΔEbind | |
|---|---|---|---|---|---|---|---|---|---|---|
| H | 2.315 | –0.477 | 130.5 | –283.4 | –95.3 | –3.0 | –67.5 | –9.8 | –248.7 | |
| NH2 | o- | 2.316 | –0.482 | 130.4 | –282.6 | –94.4 | –3.1 | –67.0 | –9.4 | –247.4 |
| m- | 2.317 | –0.486 | 131.8 | –278.3 | –95.8 | –3.0 | –68.5 | –9.7 | –243.6 | |
| p- | 2.320 | –0.492 | 128.4 | –275.0 | –92.5 | –3.0 | –65.2 | –10.1 | –240.0 | |
| NO2 | o- | 2.301 | –0.444 | 135.0 | –289.8 | –100.4 | –2.8 | –70.9 | –10.4 | –255.5 |
| m- | 2.308 | –0.460 | 135.2 | –288.7 | –100.7 | –2.9 | –72.4 | –9.9 | –256.0 | |
| p- | 2.309 | –0.462 | 131.9 | –289.8 | –98.0 | –3.0 | –69.0 | –10.7 | –255.5 | |
| X-P | Pt–Ow | q(w) | ΔEPauli | ΔEelst | ΔEorb | ΔEdisp | ΔEorbσ | ΔEorbπ | ΔEbind | |
|---|---|---|---|---|---|---|---|---|---|---|
| H | 2.137 | 0.177 | 60.9 | –64.4 | –37.9 | –3.0 | –27.9 | –5.9 | –46.8 | |
| NH2 | o- | 2.141 | 0.174 | 60.1 | –63.2 | –37.0 | –3.0 | –27.3 | –5.7 | –45.6 |
| m- | 2.141 | 0.172 | 60.7 | –63.4 | –36.9 | –3.0 | –27.2 | –5.7 | –45.2 | |
| p- | 2.147 | 0.170 | 59.3 | –62.3 | –36.1 | –2.9 | –26.6 | –5.5 | –44.4 | |
| NO2 | o- | 2.116 | 0.191 | 64.1 | –67.6 | –40.7 | –3.1 | –29.7 | –6.5 | –49.7 |
| m- | 2.131 | 0.183 | 63.5 | –66.2 | –39.8 | –3.0 | –29.2 | –6.2 | –48.6 | |
| p- | 2.130 | 0.182 | 61.5 | –65.6 | –39.1 | –3.0 | –28.8 | –6.2 | –48.6 | |
a
All energy values are in kcal/mol. The data for all X’s are shown in Table S2.
b
ΔEbind energies were calculated at the B3LYP-D3BJ/BS2//B3LYP/BS1 level.