Table 2.
Energetic effect of the cyclohexane environment on the important structures discussed in the gas phase sections.
| In the gas phase | In cyclohexane | Solvent effect | |||||
|---|---|---|---|---|---|---|---|
| ∆Hr a | ∆Gr a | ∆Hrch a | ∆Grch a | ∆∆Hr b | ∆∆Gr b | ||
| kJ·mol–1 | kJ·mol–1 | kJ·mol–1 | kJ·mol–1 | kJ·mol–1 | kJ·mol–1 | ||
| Dimer | |||||||
| (HStLi)2(1-a) (with respect to (HStLi)2(1-a)) | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 | |
| (HStLi)2(1-c) (with respect to (HStLi)2(1-a)) | 10.7 | 10.8 | 9.4 | 10.9 | 1.3 | −0.1 | |
| (HSt2Li)2(9-f) (with respect to (HSt2Li)2(9-b)) | 25.8 | 15.8 | 22.0 | 8.1 | 3.8 | 7.7 | |
| Monomer (Dissociation energy) | |||||||
| HStLi(2-c) (with respect to 1/2[(HStLi)2(1-a)]) | 106.7 | 81.8 | 76.8 | 52.6 | 29.9 | 29.2 | |
| HStLi(2-a) (with respect to 1/2[(HStLi)2(1-a)]) | 113.0 | 88.3 | 76.5 | 51.2 | 36.5 | 37.1 | |
| HSt2Li(10-f) (with respect to 1/2[(HSt2Li)2(9-b)]) | 122.2 | 90.0 | 90.4 | 56.4 | 31.8 | 33.6 | |
| Reaction | |||||||
| System(s-4-d) (St/[HStLi(2-c)]) | Transition state (4-d) | 50.4 | 82.4 | 51.1 | 85.7 | −0.7 | −3.3 |
| Precursor complex (5-a) | 24.2 | 51.9 | 24.4 | 51.6 | −0.2 | 0.3 | |
| System(s-4-a) (St/[HStLi(2-a)]) | Transition state (4-a) | 69.1 | 100.6 | 66.4 | 100.3 | 2.7 | 0.3 |
| Precursor complex (6-a) | 36.9 | 62.5 | 34.1 | 60.8 | 2.8 | 1.8 | |
| System(s-11-g) (St/[HSt2Li(10-f)]) | Transition state (11-g) | 63.9 | 89.6 | 63.5 | 92.2 | 0.4 | −2.6 |
| Precursor complex (13-a) | 37.7 | 59.2 | 36.5 | 53.9 | 1.2 | 5.3 | |
a ∆Hr and ∆Gr are the relative enthalpy and relative free energy in the gas phase, respectively. ∆Hrch and ∆Grch are the relative enthalpy and relative free energy in cyclohexane, respectively; b ∆∆Hr = ∆Hr − ∆Hrch. ∆∆Gr = ∆Gr − ∆Grch.