Table 4.
Thermodynamic and Kinetic Data for HAT Reactions of [CuOH]2+ Complexes with 9,10-Dihydroanthracene (DHA) and 1,4-Cyclohexadiene (CHD) at −25 °C in DFB
| compound | ligand | ΔBDEDHA (kcal mol−1)a | kDHA (M−1 s−1) | kH/kD (DHA) | kCHD (M−1 s−1) | ΔBDECHD (kcal mol−1)a |
|---|---|---|---|---|---|---|
| 8a | SO3L4− | 14.7 | 400(22) | 12 | 70(8) | 15 |
| 8a′b | SO3L4− | 14.7 | 500(30) | − | 90(9) | 15 |
| 9a | NMe3L | 14.7 | 2.8(7) | 18c | 28(2) | 15 |
| 2ad | pyrL2− | 13.7 | 50(8) | 27e | 38(2)f | 14 |
| 2bd | NO2L2− | 14.7 | 346(50) | 10e | − | 15 |
| 2cd | pipL2− | 11.7 | 25(4) | 17e | − | 12 |
a
Calculated as the difference between the O−H BDE of the product [Cu(OH2)]2+ complex and the BDE of the substrate C−H bond (taken from ref 30).
b
100 eq. of [Na(15-crown-5)]OTf added.
c
For this value kD is taken as the average of the kD values measured at 243 and 253 K (see Figure S33).
d
From ref 4 unless otherwise stated.
e
Extrapolated values, determined from activation parameters reported in ref 4 measured in CH2Cl2.
f
From ref 31.