15CL 353.15 2.3 93054 16CL 353.15 11.9 93885 353.15 5.1 94372 17CL 18CL 353.15 3.2 96333 12CL 353.15 2.5 96988 13CHO 353.15 2.3 90251 14CHO-TS 353.15 42.7 15CHO 353.15 -8.9 99010 12CL 353.15 2.5 96988 353.15 9.8 96987 14CO2-TS 353.15 10.9 98474 15CO2 353.15 9.9 16CO2-TS 353.15 11.4 98232 17CO2 353.15 -9.2 98414 18CO2 353.15 -9.6 99732 353.15 -7.6 99607 20CO2 353.15 17.7 99539 21CO2 353.15 -6.8 DFT protocol: # rwb97xd/6-31G(d) scrf=(cpcm,solvent=dichloromethane) NoSymm temperature=353.15 K Figure S8: Potential energy surface for propagation (green); CHO/CO2 ROCOP (purple) -CL or CHO ROP (blue); DFT protocol: # rwb97xd/6-31g(d) scrf=(cpcm,solvent=dichloromethane) NoSymm temperature=353.15 K, as per Table S4. Data available <please insert link to10.14469/hpc/278> Figure S9: 1H NMR spectrum of PCL before the 2nd addition of and 6.0 ε-CL h after the 2nd addition of (lower) at room temperature. The signal of CHO is ε-CL used as the internal reference. # [cat.]/[ε-CL]/[CHO] Temp. t (h) Mn (kDa) Đ (oC) a 1/100/900 80 2.0 8.8 1.43
15CL 353.15 2.3 93054 16CL 353.15 11.9 93885 17CL 353.15 5.1 94372 18CL 353.15 3.2 96333 12CL 353.15 2.5 96988 13CHO 353.15 2.3 90251 14CHO-TS 353.15 42.7 15CHO 353.15 -8.9 99010 12CL 353.15 2.5 96988 353.15 9.8 96987 14CO2-TS 353.15 10.9 98474 15CO2 353.15 9.9 16CO2-TS 353.15 11.4 98232 17CO2 353.15 -9.2 98414 18CO2 353.15 -9.6 99732 353.15 -7.6 99607 20CO2 353.15 17.7 99539 21CO2 353.15 -6.8 DFT protocol: # rwb97xd/6-31G(d) scrf=(cpcm,solvent=dichloromethane) NoSymm temperature=353.15 K Figure S8: Potential energy surface for -CL propagation (green); CHO/CO2 ROCOP (purple) or CHO ROP (blue); DFT protocol: # rwb97xd/6-31g(d) scrf=(cpcm,solvent=dichloromethane) NoSymm temperature=353.15 K, as per Table S4. Data available <please insert link to10.14469/hpc/278> Figure S9: 1H NMR spectrum of PCL before the 2nd addition of ε-CL and 6.0 h after the 2nd addition of ε-CL (lower) at room temperature. The signal of CHO is used as the internal reference. # [cat.]/[ε-CL]/[CHO] Temp. (oC) t (h) Mn (kDa) Đ a 1/100/900 80 2.0 8.8 1.43
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