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1 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry 2011 Phosphoric and Phosphoramidic Acids as Bifunctional atalysts for the Ring-pening Polymerization of - aprolactone: A ombined Experimental and Theoretical Study Damien Delcroix, a Aline ouffin, a Nicolas Susperregui, b hristophe Navarro, c Laurent Maron, *,b Blanca Martín Vaca *,a and Didier Bourissou *,a a University of Toulouse, UPS, LFA,118 route de Narbonne, F Toulouse (France) and NRS, LFA UMR 5069, F Toulouse (France). b University of Toulouse, INSA, UPS, LPN, 135 avenue de Rangueil, F Toulouse (France) and NRS, LPN UMR 5215, F Toulouse (France). c Arkema, Lacq Research enter, Po Box 34, Lacq (France) Electronic Supplementary Information ontents: Synthesis of phosphoramidic acid PAA Figures S1-S5 omputational results (All energies in are absolute) S2 S3 S6 -S1-

2 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry 2011 Synthesis of phosphoramidic acid PAA: Diphenylphosphochloridate (1.1 ml, 5.3 mmol, 1 equiv.) was dissolved in DM (20 ml). Triethylamine NEt 3 (5.1 ml, 36.8 mmol, 7 equiv.) was added at 0. DMAP (1.28 g, 10.5 mmol, 2 equiv.) and trifluoromethanesulfonamide TfN 2 (940 mg, 6.3 mmol, 1.2 equiv.) were then added to the reaction mixture at 0. The cold bath was removed and the reaction mixture was stirred for 2 hours at room temperature, and then heated at reflux for 1 hour. The total conversion of phosphochloridate was monitored by 31 P NMR spectroscopy: disappearance of the signal for the starting material at 7.2 ppm and appearance of a new singlet at 12.9 ppm. DM (15mL) was then added and the organic layer was washed with water (20 ml). The organic layer was washed with a hydrochloric acid solution (37%) until no traces of triethylamine and DMAP were observed in the 1 NMR spectrum. The organic layer was then dried over Na 2 S 4, filtered and the solvent was removed under vacuum. The resulting white solid was dissolved in DM and cooled to 30 to give white crystals (m = 0.89 g, Yield = 60%). 19 F NMR (Dl 3, 282 Mz): 76.9 (s) ppm. 31 P NMR (Dl 3, 203 Mz): 16.4 (s) ppm. 1 NMR (Dl 3, 300 Mz): 8.30 (br s, 1, N), 7.10 (m, 2 x 5, 6 5 ) ppm. 13 NMR (Dl 3, 75 Mz): (2 x ), (), (2 x ), (q, 1 J -F = z, F 3 ) ppm. Mp = S2-

3 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry 2011 (a) (b) Figure S1 (a) 1 NMR spectrum (Dl 3, 300 Mz) and (b) MALDI-TF MS (region m/z 1000 to 6000 g/mol) of a PL ([ε-l] 0 /[n-pent] 0 /[PA] = 40/1/1, ([ε-l] 0 = 0.9 mol/l, toluene, 30 ). Figure S2. (a) Plot of M n(se) (estimated by SE and a correction factor of 0.56) vs ε-l conversion ([ε-l] 0 /[n-pent] 0 /[PA] = 40/1/1, toluene, 30 ). (b) Semi-logarithmic plot ([ε- L] 0 /[n-pent] 0 /[PA] = 40/1/1, toluene, 30 ). -S3-

4 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry ppm (t1) Figure S3 (a) 1 NMR spectrum (Dl 3, 300 Mz) of a PL ([ε-l] 0 /[n-pent] 0 /[PAA] = 80/1/1, ([ε-l] 0 = 0.9 mol/l, toluene, 30 ) a) * * * * b) * * * * * * * * * Figure S4 (a) MALDI-TF MS (region m/z to g/mol) of a PL ([ε-l] 0 /[n- Pent] 0 /[PA] = 80/1/1, toluene, 30, [ε-l] 0 = 0.9 mol/l) and (b) MALDI-TF MS (region m/z to g/mol) of a PL ([ε-l] 0 /[n-pent] 0 /[PAA] = 80/1/1, toluene, 30, [ε-l] 0 = 0.9 mol/l). Main population M = n 114 (M ε-l ) + 18 (M Pent ) + 23 (M Na+ ) g/mol. * Second population M = n 114 (M ε-l ) + 18 (M 2 ) + 23 (M Na+ ) g/mol -S4-

5 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry ppm (t1) Figure S5 (a) 1 NMR spectrum (Dl 3, 300 Mz) of a PL ([ε-l] 0 /[n-pent] 0 /[PAA] = 80/1/3, ([ε-l] 0 = 2.7 mol/l, toluene, 60 ) S5-

6 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry 2011 Reaction of ε-l with methanol catalyzed by phosphoric acid PA G (kcal/mol) nucleophilic addition ring-opening +40 TS" 1 (+40.1) TS" 2 (+46.7) TS' 1 (+32.1) TS 1 (+17.8) (+15.1) TS' 2 (+25.5) +10 (+9.6) (+7.6) TS 2 (+14.6) (+7.5) (+6.1) 0 ternary adduct of reactants R tetrahedral intermediate TI (0.3) binary adduct of products P Ternary adduct of reactant R Energy: P S

7 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry 2011 Bifunctional pathway involving the acidic proton and the basic P= moiety of PA Tetrahedral intermediate Energy: P Ring-opened product Energy: P S7-

8 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry 2011 Transition state for the nucleophilic addition TS 1 Energy: P Transition state for the ring-opening TS 2 Energy: P S8-

9 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry 2011 Bifunctional pathway involving the acidic proton and oxygen atom of the P moiety of PA Tetrahedral intermediate Energy: Ring-opened product Energy: P P S9-

10 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry 2011 Transition state for the nucleophilic addition TS' 1 Energy: P Transition state for the ring-opening TS' 2 Energy: P S10-

11 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry 2011 Monofunctional pathway: activation by the acidic proton of PA Tetrahedral intermediate Energy: P Ring-opened product Energy: P S11-

12 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry 2011 Transition state for the nucleophilic addition TS" 1 Energy: P Transition state for the ring-opening TS" 2 Energy: P S12-

13 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry 2011 Reaction of ε-l with methanol catalyzed by the phosphoramidic acid PAA Ternary adduct of reactant R Energy: P N S S F F F

14 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry 2011 Bifunctional pathway involving the acidic proton and the basic P= moiety of PAA Tetrahedral intermediate Energy: P N S F F F Ring-opened product Energy: P S14-

15 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry 2011 Transition state for the nucleophilic addition TS 3 Energy: P N S F F F Transition state for the ring-opening TS 4 Energy: P N S F F F S15-

16 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry 2011 Bifunctional pathway involving the acidic proton and the basic S= moiety of PAA Tetrahedral intermediate Energy: P N S F F F Ring-opened product Energy: P N S F F F S

17 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry 2011 Transition state for the nucleophilic addition TS' 3 Energy: F S N F F P Transition state for the ring-opening TS' 4 Energy: -1910, P N S F F F S17-

18 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry 2011 Monofunctional pathway: activation by the acidic proton of PAA Tetrahedral intermediate Energy: P N Ring-opened product Energy: P N S F F F S S F F F

19 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry 2011 Transition state for the nucleophilic addition TS" 3 Energy: P N S F F F Transition state for the ring-opening TS" 4 Energy: P N S F F F S

20 Electronic Supplementary Material (ESI) for Polymer hemistry This journal is The Royal Society of hemistry S20-