Table 3. First and Second Proton Affinities (PAs)a and Bond Dissociation Energies Including ZPE Corrections of 1–6 with One and Two W(CO)5 and HNMe2 (D0)b,c,d,e.
|
n = 1 |
n = 2 |
|||||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| system | PA/D0 | 6s Bi | 6pz Bi | π L | OS Bi | OS L | R (%) | PA/D0 | 6s Bi | 6pz Bi | π L | OS Bi | OS L | R (%) |
| 1-(H+)n | 244.2 | 0.92 | 0.34 | <0.05 | +3 | –1 | 75.8 | 103.1 | 0.69 | 0.33 | <0.05 | +3 | –1 | 50.0 |
| 1-(W(CO)5)n | 48.1 | 0.92 | 0.53 | 0.20 | +1 | –1 | 71.0 | 33.2 | 0.87 | 0.55 | 0.13 | +1 | –1 | 78.3 |
| 2-(H+)n | 243.3 | 0.92 | 0.35 | <0.05 | +3 | –1 | 75.4 | 94.4 | 0.69 | 0.33 | <0.05 | +3 | –1 | 50.0 |
| 2-(W(CO)5)n | 52.0 | 0.92 | 0.54 | 0.19 | +1 | –1 | 73.4 | 37.1 | 0.88 | 0.53 | 0.10 | +1 | –1 | 77.7 |
| 3-(H+)n | 249.6 | 0.92 | 0.36 | <0.05 | +3 | –1 | 75.5 | 114.5 | 0.70 | 0.34 | <0.05 | +3 | +1 | 53.6 |
| 3-(W(CO)5)n | 53.4 | 0.92 | 0.55 | 0.18 | +1 | –1 | 74.1 | 44.1 | 0.87 | 0.52 | 0.10 | +1 | –1 | 76.5 |
| 4-(H+)n | 220.4 | 0.90 | 0.34 | <0.05 | +3 | –1 | 75.9 | 98.4 | 0.68 | 0.33 | <0.05 | +3 | –1 | 71.6 |
| 4-(W(CO)5)n | 38.7 | 0.90 | 0.48 | 0.31 | +1 | –1 | 65.6 | 34.5 | 0.88 | 0.51 | 0.18 | +1 | –1 | 80.2 |
| 4-(HNMe2)n | 12.1 | 0.90 | 0.28 | 0.74 | +3 | –3 | 97.4 | 16.4 | 0.88 | 0.18 | 0.87 | +3 | –3 | 100 |
| 5-(H+)n | 188.0 | 0.91 | 0.36 | <0.05 | +3 | –1 | 73.7 | 62.5 | 0.69 | 0.34 | <0.05 | +3 | –1 | 67.6 |
| 5-(W(CO)5)n | 27.8 | 0.91 | 0.46 | 0.38 | +1 | –1 | 56.1 | 30.7 | 0.88 | 0.51 | 0.20 | +1 | –1 | 77.0 |
| 5-(HNMe2)n | 20.4 | 0.91 | 0.23 | 0.85 | +3 | –3 | 100 | 21.2 | 0.88 | 0.18 | 0.91 | +3 | –3 | 100 |
| 6-(H+)n | 229.1 | 0.90 | 0.35 | <0.05 | +3 | –1 | 76.4 | 100.5 | 0.69 | 0.33 | <0.05 | +3 | –1 | 72.8 |
| 6-(W(CO)5)n | 41.9 | 0.90 | 0.51 | 0.25 | +1 | –1 | 73.0 | 39.7 | 0.86 | 0.52 | 0.13 | +1 | –1 | 76.7 |
| 6-(HNMe2)n | 8.0 | 0.90 | 0.36 | 0.63 | +3 | –3 | 77.3 | 11.3 | 0.88 | 0.21 | 0.83 | +3 | –3 | 100 |
a
The proton affinities are defined as PA1 = ΔH(1–6) + ΔH(H+) – ΔH(1–6-(H+)) and PA2 = ΔH(1–6-(H+)) + ΔH(H+) – ΔH(1–6-(H+)2) as described in ref (54). Proton enthalpy +1.5 kcal/mol.
b
Frontier EFOs occupations (in au) of Bi and the pincer ligand (NCN or NNN) and assigned oxidation states.
c
All calculations were performed at the B3LYP-D3(BJ)/def2-TZVPP level of theory.
d
All energies are in kcal/mol.
e
Three pseudodegenerated EFOs (in occupation), one from the NCN pincer ligand and two from H atoms (one each).