Supporting information The chemical shifts at room temperature of the main 1H NMR lines for the starting materials and the decomposition products for the thermolysis of 1a and of 2a in C6D6. 1 H NMR (200 MHz, C6D6, 7.16 ppm): 1a 1.09a (s, 6H), 1.24 (s, 6H), 1.40 (br, 6H), 1.57 (br s, 6H), 6.79 (dt, J = 9.2 Hz, 2H), 7.74 (dt, J = 9.2 Hz, 2H); 2a 1.32 (br s, 6H), 7.7 (d, J = 9.2 Hz, 2H); 4 1.17 (s, 12H), 1.35 (br, 6H), 3.66 (br s, 1H); 6 3.2 (br s, 1H); 7d 4.22 (br s, 1H); 8e 1.38 (s, 12H); 9b 1.02 (dt, J = 7.06 Hz, 6H), 2.37 (septet, J = 7.06 Hz, 1H); 10c 1.78 (br, 3H), 5.25 (br, 1H), 6.12 (br, 1H), 6.60 (dt, J = 9.2 Hz, 2H), 7.70 (dt, J = 9.2 Hz, 2H); 11 1.36 (s, 6H). a The values of the integrals of the underlined NMR peaks were used to determine the amount of compounds. bIdentified from the 1H NMR pattern, i.e., septet for the CH, and doublet for CH3. c was observed during the decomposition of TEMPO-PEstMe in C6D6 in the absence of scavenger. d From authentic sample kindly provided by Prof. Grecci. e For reference see 9. . 1