Bond dissociation energies (BDEs) for O1–O1′ and C2–C4 bonds of RC(O)O–OC(O)R peroxides, labeled BDE(O–O, peroxide) and BDE(C–C, peroxide), respectively, and BDE for the C2–C4 bond of RC(O)O˙ radicals, labeled BDE(C–C, radical) (in kJ mol−1).
| R . | BDE(O–O, peroxide)a . | BDE(C–C, peroxide)b . | BDE(C–C, radical)a . |
|---|---|---|---|
| CH3 | 234.1 (219.0) | 457.7 | −106.9 (−124.8) |
| CH2F | 228.9 (215.0) | 423.9 | −127.4 (−140.8) |
| CHF2 | 230.2 (216.5) | 396.2 | −143.3 (−151.6) |
| CF3 | 231.0 (218.2) | 396.5 | −139.8 (−145.0) |
| CH2–CH3 | 234.4 (220.3) | 457.7 | −106.3 (−122.1) |
| CH2–CH2F | 235.5 (221.7) | 459.8 | −104.4 (−120.0) |
| CH2–CHF2 | 236.7 (223.2) | 461.7 | −105.0 (−118.8) |
| CH2–CF3 | 237.9 (224.2) | 454.1 | −114.0 (−127.6) |
| CHF–CH3 | 248.0 (233.8) | 431.1 | −132.5 (−143.0) |
| CHF–CH2F | 251.3 (237.2) | 434.3 | −136.2 (−145.9) |
| CHF–CHF2 | 241.9 (228.2) | 431.6 | −132.6 (−142.2) |
| CHF–CF3 | 239.5 (226.4) | 423.4 | −136.7 (−146.1) |
| CF2–CH3 | 232.9 (220.0) | 408.9 | −136.5 (−142.7) |
| CF2–CH2F | 227.6 (214.7) | 407.3 | −132.0 (−138.0) |
| CF2–CHF2 | 233.3 (220.3) | 405.4 | −138.1 (−143.3) |
| CF2–CF3 | 234.4 (221.6) | 403.4 | −142.1 (−147.1) |
| R . | BDE(O–O, peroxide)a . | BDE(C–C, peroxide)b . | BDE(C–C, radical)a . |
|---|---|---|---|
| CH3 | 234.1 (219.0) | 457.7 | −106.9 (−124.8) |
| CH2F | 228.9 (215.0) | 423.9 | −127.4 (−140.8) |
| CHF2 | 230.2 (216.5) | 396.2 | −143.3 (−151.6) |
| CF3 | 231.0 (218.2) | 396.5 | −139.8 (−145.0) |
| CH2–CH3 | 234.4 (220.3) | 457.7 | −106.3 (−122.1) |
| CH2–CH2F | 235.5 (221.7) | 459.8 | −104.4 (−120.0) |
| CH2–CHF2 | 236.7 (223.2) | 461.7 | −105.0 (−118.8) |
| CH2–CF3 | 237.9 (224.2) | 454.1 | −114.0 (−127.6) |
| CHF–CH3 | 248.0 (233.8) | 431.1 | −132.5 (−143.0) |
| CHF–CH2F | 251.3 (237.2) | 434.3 | −136.2 (−145.9) |
| CHF–CHF2 | 241.9 (228.2) | 431.6 | −132.6 (−142.2) |
| CHF–CF3 | 239.5 (226.4) | 423.4 | −136.7 (−146.1) |
| CF2–CH3 | 232.9 (220.0) | 408.9 | −136.5 (−142.7) |
| CF2–CH2F | 227.6 (214.7) | 407.3 | −132.0 (−138.0) |
| CF2–CHF2 | 233.3 (220.3) | 405.4 | −138.1 (−143.3) |
| CF2–CF3 | 234.4 (221.6) | 403.4 | −142.1 (−147.1) |
Values in parentheses are corrected with zero point energy.
Geometry of each fragment is frozen to that in the parent peroxide.