Table 2. Pt–pyrX Interaction (X = H, NH2, NO2) in the Gas Phase Optimized X-R, X-TS, and X-P Structures: Pt–NpyrX Bond Lengths (in Å); Total NPA Charges of the Pt Atom (q(Pt)) and pyrX Ligands (q(pyrX)) (in e); and ETS-NOCV Energy Decomposition Terms ΔEPauli, ΔEelst, ΔEorb, ΔEdisp, ΔEorbσ, and ΔEorb Obtained at the BLYP-D3BJ/TZ2P//B3LYP/BS1 Levela.
| Pt–NpyrX | q(Pt) | q(pyrX) | ΔEPauli | ΔEelst | ΔEorb | ΔEdisp | ΔEorbσ | ΔEorbπ | ΔEbind | ||
|---|---|---|---|---|---|---|---|---|---|---|---|
| X-R | |||||||||||
| H | 2.081 | 0.617 | 0.241 | 127.6 | –122.5 | –61.6 | –7.2 | –40.7 | –11.6 | –65.7 | |
| NH2 | o- | 2.086 | 0.601 | 0.257 | 135.6 | –129.9 | –64.5 | –9.0 | –41.2 | –10.9 | –69.9 |
| m- | 2.078 | 0.616 | 0.254 | 129.7 | –127.4 | –63.4 | –7.4 | –41.8 | –10.3 | –70.4 | |
| p- | 2.077 | 0.612 | 0.268 | 130.5 | –131.0 | –64.0 | –7.3 | –42.5 | –12.1 | –73.8 | |
| NO2 | o- | 2.111 | 0.613 | 0.205 | 114.4 | –103.3 | –57.7 | –10.2 | –34.7 | –11.6 | –57.5 |
| m- | 2.089 | 0.618 | 0.220 | 120.3 | –108.0 | –59.5 | –7.3 | –38.0 | –10.4 | –55.6 | |
| p- | 2.084 | 0.618 | 0.221 | 122.8 | –109.6 | –60.6 | –7.2 | –38.6 | –12.7 | –57.5 | |
| X-TS | |||||||||||
| H | 2.046 | 0.791 | 0.294 | 174.2 | –147.2 | –78.6 | –7.6 | –53.4 | –12.5 | –62.7 | |
| NH2 | o- | 2.050 | 0.770 | 0.312 | 192.7 | –160.6 | –85.9 | –9.8 | –57.4 | –12.5 | –67.1 |
| m- | 2.044 | 0.789 | 0.304 | 176.9 | –152.4 | –80.8 | –7.8 | –54.8 | –10.7 | –67.5 | |
| p- | 2.043 | 0.784 | 0.319 | 177.0 | –155.4 | –81.5 | –7.7 | –55.7 | –12.7 | –71.1 | |
| NO2 | o- | 2.072 | 0.799 | 0.243 | 159.6 | –128.2 | –73.2 | –10.7 | –45.6 | –12.5 | –54.5 |
| m- | 2.053 | 0.797 | 0.269 | 166.8 | –133.1 | –75.8 | –7.7 | –49.8 | –10.9 | –52.5 | |
| p- | 2.050 | 0.799 | 0.268 | 169.6 | –134.8 | –77.1 | –7.6 | –50.5 | –13.7 | –52.4 | |
| X-P | |||||||||||
| H | 2.011 | 0.749 | 0.424 | 147.3 | –153.1 | –101.7 | –7.5 | –64.2 | –19.6 | –114.3 | |
| NH2 | o- | 2.016 | 0.736 | 0.439 | 152.7 | –159.0 | –105.1 | –9.5 | –63.9 | –18.9 | –120.4 |
| m- | 2.007 | 0.745 | 0.437 | 151.0 | –162.4 | –105.8 | –7.7 | –66.0 | –19.3 | –123.7 | |
| p- | 2.005 | 0.738 | 0.450 | 152.6 | –168.4 | –107.5 | –7.6 | –66.8 | –22.3 | –130.0 | |
| NO2 | o- | 2.038 | 0.780 | 0.369 | 131.8 | –128.7 | –97.0 | –10.1 | –55.2 | –19.1 | –102.7 |
| m- | 2.016 | 0.757 | 0.404 | 139.4 | –132.5 | –100.1 | –7.6 | –61.4 | –19.6 | –99.3 | |
| p- | 2.014 | 0.757 | 0.404 | 141.0 | –133.1 | –100.1 | –7.5 | –61.5 | –21.1 | –98.6 | |
a
ΔEbind energy values were calculated at the B3LYP-D3BJ/BS2//B3LYP/BS1 level. All energy values are in kcal/mol. The data for all X’s are shown in Table S1.