Table 2. EDA-NOCV results of the analysis of Pt–Pb bonds in 2, 8a and 11 at the D3(BJ) + BP86/TZ2P//RI-D3(BJ)-BP86/def2-TZVP + def2-QZVP level (kcal mol–1).
| Compound | 2 | 2 | 8a | 8a | 11 | 11 |
| Fragmentation pattern | D c | E c | D c | E c | D c | E c |
| Fragment 1 | [(Cy3P)2Pt] | [Cy3P]2Pt+ | [(Cy3P)2Pt] | [(Cy3P)2Pt]+ | [(Cy3P)2Pt] | [(Cy3P)2Pt]+ |
| Fragment 2 | [PbCl2–PbCl2–Pt(PCy3)2] | [PbCl2–PbCl2–Pt(PCy3)2]– | [PbCl–PbCl–Pt(PCy3)2]2+ | [PbCl–PbCl–Pt(PCy3)2]+ | [Cl4Al–Pb–AlCl4] | [Cl4Al–Pb–AlCl4]– |
| ΔE int | –68.3 | –176.0 | –128.1 | –77.1 | –120.5 | –163.9 |
| ΔE Pauli | 146.9 | 169.5 | 173.7 | 192.9 | 200.5 | 249.7 |
| ΔE elstat a | –104.7 (48.7%) | –183.1 (53.0%) | –124.2 (41.2%) | –112.7 (41.7%) | –139.9 (43.6%) | –246.5 (59.6%) |
| ΔE disp a | –44.7 (20.8%) | –44.7 (12.9%) | –50.1 (16.6%) | –50.1 (18.5%) | –49.8 (15.5%) | –49.8 (12.0%) |
| ΔE orb a | –65.7 (30.5%) | –117.7 (34.1%) | –127.5 (42.2%) | –107.3 (39.7%) | –131.4 (40.9%) | –117.4 (28.4%) |
| ΔE σ b Pt → Pb | –32.6 (49.6%) | — | –65.1 (51.1%) | — | –60.2 (45.8%) | — |
| ΔE σ b Pt–Pb | — | –87.2 (74.1%) | — | –67.5 (62.9%) | — | –70.1 (59.7%) |
| ΔE π‖ b Pt → Pb | –7.1 (10.8%) | –2.4 (2.0%) | –9.7 (7.6%) | –10.6 (9.9%) | –9.7 (7.4%) | –17.2 (14.7%) |
| ΔE π⊥ b Pt → Pb | –4.8 (7.3%) | –4.8 (4.1%) | –15.4 (12.1%) | –6.2 (5.8%) | –25.4 (19.3%) | –6.4 (5.5%) |
| ΔE σ b Pb → Pt | –3.8 (5.8%) | — | –5.3 (4.2%) | — | –4.0 (3.0%) | — |
| Rest b | –17.4 (26.5%) | –23.3 (19.8%) | –32.0 (25.0%) | –23.0 (21.4%) | –32.1 (24.5%) | –23.6 (20.2%) |
| ΔE prep | 12.9 | 5.1 | 37.5 | 17.3 | 52.9 | 12.3 |
| –D e | –55.4 | –170.9 | –90.6 | –59.8 | –67.6 | –151.6 |
aThe values in parentheses give the percentage contribution to the total attractive interactions ΔE elstat + ΔE disp + ΔE orb.
bThe values in parentheses give the percentage contribution to the total orbital interactions ΔE orb.
cD: donor–acceptor bonding model; E: electron sharing bonding model.