Supplementary Information Fenton s Reagent Catalysed Release of Carbon Monooxide from 1,3- Dihydroxy Acetone Tumpa Sadhukhan, a Dharitri Das, a Pratik Kalekar, b Vidya Avasare,* b and Sourav Pal,* a a Department of Chemistry, Indian Institution of Technology Bombay, Mumbai 400076, India. b Department of Chemistry, Sir Parashurambhau College, Pune-411030, India Table S1: Optimized energies, Zero point corrections (ZPE), Thermal correction to energy ( E), Thermal correction to enthalpy ( H), and Thermal correction to Gibbs free energy ( G) in atomic units obtained from M06-2X/6-311++G(d,p) methodology and in aqueous phase with dielectric constant 78.39 for H-abstraction from C α -OH, Formation of CHOCOCHO,Fragmentation of CHOCOCHO and Formation of CO and CO 2. Energy Species (<S 2 ZPE E H G >) Imag (Hz) R1: (CH 2 OHCOCH 2 OH+OH) -419.3024394 (0.753445) 0.106452 0.116301 0.117245 0.070365 - TS1-419.2872877 (0.760820) 0.100968 0.109602 0.110547 0.067014-1722.75 P1: (CH 2 OCOCH 2 OH+H 2 O) -419.3187182 (0.754099) 0.105723 0.115850 0.116795 0.069430 - R2: (CH 2 OCOCH 2 OH+OH) 418.6225172 (2.006713) 0.092327 0.101729 0.102674 0.056403 - TS2-418.606381 (2.01469) 0.086679 0.095065 0.096009 0.052252-1722.42 P2: (CH 2 OCOCH 2 O+H 2 O) -418.6382965 (2.008048) 0.091492 0.101288 0.102233 0.055137 - Pathway_a R3: (CH 2 OCOCH 2 O) -342.2013012 (2.008308) 0.067057 0.073436 0.074380 0.035572 - TS3-342.1970886 (2.008205) 0.065359 0.071666 0.072610 0.033702-471.60 P3: (CH 2 OCOCH 2 O) rot -342.2027617 (2.008572) 0.066640 0.073048 0.073992 0.035128 - R4:((CH 2 OCOCH 2 O) rot +OH) -418.0056416 (0.754068) 0.084885 0.092587 0.093531 0.051793 - TS4-417.9668452 (0.761522) 0.081340 0.087920 0.088864 0.050051-945.20 P4: ((CHOCOCH 2 O) rot +H 2 O) -418.0947151 (0.754195) 0.081743 0.091338 0.092282 0.046715 - R5: ((CHOCOCH 2 O) rot +OH) -417.4595806 0.075470 0.082875 0.083819 0.043391 - TS5-417.3690141 0.068152 0.075393 0.076337 0.036383-2231.83 P5: ((CHOCOCHO) rot +H 2 O) -417.5518728 0.071859 0.081381 0.082325 0.037337 - S1
R6: (CH 2 OCOCH 2 O+OH) TS6 P6: (CHOCOCH 2 O+H 2 O) R7: (CHOCOCH 2 O+OH) TS7 P7: (CHOCOCHO+H 2 O) R8: (CHOCOCHO) TS8 P8: (CHOCOCHO) rot R9: ((CHOCOCHO) rot +OH) TS9 P9: (CHOCO+HCOOH) TS10 P10: (CHOCOOH+CHO) R11: (CHOCOOH+OH) TS11 P11: (CHO+CO 2 +H2O) R12: (CHOCOOH) TS12 P12: (2CO+H 2 O) R13: (CHO+OH) TS13 P13: (CO+H 2 O) -418.0013314 (0.754005) -417.9668287 (0.763979) -418.0891756 (0.75388) -417.4579582-417.3697879-417.5492342-341.1076267-341.1043782-341.1118127-416.8509403 (0.752934) -416.8404683 (0.79739) -416.9367487 (0.761022) -416.8748565 (0.760339) -416.9114078 (0.753805) -378.8052543 (0.753281) -378.7901939 (0.759519) -378.8548917 (0.753336) -303.0644709-302.9470081-303.0521388-189.7570103-189.6372933-189.7405537 Pathway_b 0.084520 0.092579 0.093523 0.050729-0.081580 0.088099 0.089044 0.050271-994.27 0.080852 0.090930 0.091874 0.042328-0.075152 0.082742 0.083686 0.042673-0.068623 0.075807 0.076751 0.036794-1981.35 0.072212 0.081582 0.082526 0.037853-0.047693 0.053753 0.054697 0.017225-0.047012 0.052459 0.053403 0.017513-115.95 0.047646 0.053753 0.054697 0.016828-0.058366 0.067410 0.068354 0.023218-0.058454 0.066040 0.066984 0.026106-800.68 0.061698 0.069799 0.070743 0.027031-0.060305 0.067162 0.068106 0.028773-587.81 0.059131 0.068189 0.069133 0.022183-0.054807 0.062430 0.063374 0.021703-0.052315 0.058522 0.059466 0.021387-1619.27 0.050230 0.060855 0.061799 0.010653-0.043882 0.048691 0.049635 0.015852-0.034326 0.040107 0.041051 0.005373-1550.19 0.034529 0.044511 0.045455-0.003397-0.034248 0.037412 0.038356 0.010180-0.026047 0.030035 0.030979 0.001155-1716.00 0.027825 0.034353 0.035297-0.001097 - S2
Table S2:Optimized energies (HF), Zero point corrections (ZPE), Thermal correction to energy ( E), Thermal correction to enthalpy ( H), and Thermal correction to Gibbs free energy ( G) in atomic units obtained from M06-2X/6-311++G(d,p) methodology and in aqueous phase with dielectric constant 78.39 for Glycolate Pathway. Species Energy Imag (<S 2 ZPE E H G >) (Hz) R1: (CH 2 OHCOCH 2 OH+OH) -419.3024394 (0.753445) 0.106452 0.116301 0.117245 0.070365 - TS1-419.2872877 (0.760820) 0.100968 0.109602 0.110547 0.067014-1722.75 P1: (CH 2 OCOCH 2 OH+H 2 O) -419.3187182 (0.754099) 0.105723 0.115850 0.116795 0.069430 - R2: (CH 2 OCOCH 2 OH) -342.8823736 (0.754019) 0.080945 0.087688 0.088632 0.049567 - TS2-342.8785552 (0.754223) 0.080521 0.086574 0.087518 0.050159-64.32 P2: (CH 2 OCOCH 2 OH) rot -342.8838148 (0.754240) 0.081065 0.087791 0.088736 0.049617 - R3: ((CH 2 OCOCH 2 OH) rot +OH) -418.6862872 0.099019 0.107084 0.108028 0.066230 - TS3-418.5941091 0.091448 0.099288 0.100232 0.059174-2357.14 P3: (CHOCOCH 2 OH+H 2 O) -418.7770562 0.095226 0.105568 0.106513 0.059611 - R4: (CHOCOCH 2 OH +OH) -418.0775289 (0.752849) 0.081797 0.091491 0.092435 0.046112 - TS4-418.0656252 (0.777762) 0.083042 0.091185 0.092129 0.049498-602.68 P4: (HCOOH+COCH 2 OH) -418.1351954 (0.753473) 0.084999 0.094470 0.095414 0.048300 - TS5-418.0867435 (0.760639) 0.085285 0.092520 0.093464 0.052969-404.69 P5: (CH 2 OHCOOH+CHO) -418.1319994 (0.753286) 0.082474 0.092344 0.093288 0.044922 - R6: (CH 2 OHCOOH +OH) -380.0297627 (0.75269) 0.079075 0.087063 0.088007 0.045715 - TS6-380.0132435 (0.76077) 0.073555 0.080455 0.081399 0.041957-1734.27 P6: (CH 2 OCOOH +H 2 O) -380.0464724 (0.753965) 0.077770 0.086245 0.087190 0.043468 - R7: (CH 2 OCOOH) -303.6094284 (0.753957) 0.053334 0.058425 0.059369 0.024332 - TS7-303.6043714 (0.75414) 0.053158 0.057518 0.058462 0.025097-102.52 P7: (CH 2 OCOOH)rot -303.6083462 (0.754062) 0.053192 0.057491 0.058435 0.025226 - R8: (CH 2 OCOOH rot +OH) -379.4104888 0.071908 0.078165 0.079109 0.041633 - TS8-379.3170346 0.063842 0.070042 0.070986 0.033870-2394.59 S3
P8: (CHOCOOH+H 2 O) -379.4997077 0.067964 0.076357 0.077301 0.034389 - Figure S1: Optimized structures for H-abstraction from C α -OH, Formation of CHOCOCHO,Fragmentation of CHOCOCHO and Formation of CO and CO 2 Reactant TS Products R1 TS1 P1 R2 TS2 P2 R3 TS3 P3 R4 TS4 P4 R5 TS5 P5 S4
R6 TS6 P6 R7 TS7 P7 R8 TS8 P8 R9 TS9 P9 R10 (P9) TS10 P10 R11 TS11 P11 S5
R12 TS12 P12 R13 TS13 P13 Figure S2: Optimized structures for Glycolate Pathway. Reactant TS Products R1 TS1 P1 R2 TS2 P2 R3 TS3 P3 R4 TS4 P4 S6
R5 (P4) TS5 P5 R6 TS6 P6 R7 TS7 P7 R8 TS8 P8 Table S3: Energies calculated at CCSD(T)//M06 2X/6-311++G(d, p) level of theory in atomic units and in aqueous phase with dielectric constant 78.39 for H-abstraction from C α - OH, Formation of CHOCOCHO,Fragmentation of CHOCOCHO and Formation of CO and CO 2. Species CCSD(T) R1: (CH 2 OHCOCH 2 OH+OH) -418.4898336 TS1-418.4620879 P1: (CH 2 OCOCH 2 OH+H 2 O) -418.5056807 R2: (CH 2 OCOCH 2 OH+OH) -417.6849341 TS2-417.7805915 P2: (CH 2 OCOCH 2 O+H 2 O) -417.8281437 R3: (CH 2 OCOCH 2 O) -341.5270647 TS3-341.51787 P3: (CH 2 OCOCH 2 O) rot -341.522135 R4:((CH 2 OCOCH 2 O) rot +OH) -417.1868009 TS4-417.1493305 S7
P4: ((CHOCOCH 2 O) rot +H 2 O) -417.2782903 R5: ((CHOCOCH 2 O) rot +OH) -416.6524941 TS5-416.5641824 P5: ((CHOCOCHO) rot +H 2 O) -416.7502921 R6: (CH 2 OCOCH 2 O+OH) -417.190068 TS6-417.1502688 P6: (CHOCOCH 2 O+H 2 O) -417.2788965 R7: (CHOCOCH 2 O+OH) -416.6514685 TS7-416.5626333 P7: (CHOCOCHO+H 2 O) -416.7471123 R8: (CHOCOCHO) -340.4433838 TS8-340.4409 P8: (CHOCOCHO) rot -340.4474514 R9: ((CHOCOCHO) rot +OH) -415.9811916 TS9-416.0414785 P9: (CHOCO+HCOOH) -416.1245874 TS10-416.0614527 P10: (CHOCOOH+CHO) -416.1084174 R11: (CHOCOOH+OH) -378.0899617 TS11-378.0700495 P11: (CHO+CO 2 +H2O) -378.1444126 R12: (CHOCOOH) -302.4823628 TS12-302.3654952 P12: (2CO+H 2 O) -302.4894415 R13: (CHO+OH) -189.3964444 TS13-189.2825103 P13: (CO+H 2 O) -189.3919289 Table S4: Energies calculated at CCSD(T)/6-311++G(d, p)//m06 2X/6-311++G(d, p) level of theory in atomic units and in aqueous phase with dielectric constant 78.39 for Glycolate Pathway. Species CCSD(T) R1: (CH 2 OHCOCH 2 OH+OH) -418.4898336 TS1-418.4620879 P1: (CH 2 OCOCH 2 OH+H 2 O) -418.5056807 R2: (CH 2 OCOCH 2 OH) -342.2052343 TS2-342.1973583 P2: (CH 2 OCOCH 2 OH) rot -342.2062294 R3: ((CH 2 OCOCH 2 OH) rot +OH) -417.8715759 TS3-417.7855520 P3: (CHOCOCH 2 OH+H 2 O) -417.9680632 R4: (CHOCOCH 2 OH +OH) -417.1928583 TS4-417.2313301 P4: (HCOOH+COCH 2 OH) -417.3251337 TS5-417.2719621 P5: (CH 2 OHCOOH+CHO) -417.3225787 S8
R6: (CH 2 OHCOOH +OH) -379.3070723 TS6-379.2862400 P6: (CH 2 OCOOH +H 2 O) -379.3234402 R7: (CH 2 OCOOH) -303.0224676 TS7-303.0187040 P7: (CH 2 OCOOH)rot -303.0213610 R8: (CH 2 OCOOH rot +OH) -378.6867578 TS8-378.6001063 P8: (CHOCOOH+H 2 O) -378.7818907 Table S5: Optimized energies, Zero point corrections (ZPE), Thermal correction to energy ( E), Thermal correction to enthalpy ( H), and Thermal correction to Gibbs free energy ( G) in atomic units obtained from B3LYP/6-311++G(d,p) methodology and in aqueous phase with dielectric constant 78.39 for H-abstraction from C α -OH, Formation of CHOCOCHO,Fragmentation of CHOCOCHO and Formation of CO and CO 2. Species Energy Imag (<S 2 ZPE E H G >) (Hz) R1: (CH 2 OHCOCH 2 OH+OH) -419.4822737 (0.754335) 0.105193 0.114763 0.115707 0.069943 - TS1-419.4753696 (0.756418) 0.099694 0.108701 0.109645 0.064933-1425.77 P1: (CH 2 OCOCH 2 OH+H 2 O) -419.4998062 (0.75405) 0.102607 0.113252 0.114196 0.064698 - R2: (CH 2 OCOCH 2 OH+OH) -418.8039051 (2.008297) 0.090886 0.100000 0.100944 0.055787 - TS2-418.7972942 (2.009942) 0.085258 0.093925 0.094869 0.050401-1427.00 P2: (CH 2 OCOCH 2 O+H 2 O) -418.82227 (2.00931) 0.088907 0.099049 0.099993 0.050819 - R3: (CH 2 OCOCH 2 O) -342.350108 (2.009133) 0.064044 0.070904 0.071848 0.031888 - TS3-342.3489923 (2.010372) 0.065316 0.071112 0.072057 0.034729-67.14 P3: (CH 2 OCOCH 2 O) rot -342.3527433 (2.009175) 0.065057 0.071687 0.072631 0.033114 - R4: (CH 2 OCOCH 2 O+OH) -418.1760103 (0.754211) 0.081901 0.090143 0.091087 0.047694 - TS4-418.1434804 (0.758658) 0.079750 0.086381 0.087326 0.048371-906.66 P4: (CHOCOCH 2 O+H 2 O) -418.2676557 (0.755403) 0.078316 0.088837 0.089781 0.039068 - R5: (CHOCOCH 2 O+OH) -417.6256793 0.073265 0.081015 0.081959 0.040404 - TS5-417.5498601 0.065787 0.073419 0.074363 0.033230-2286.58 P5: (CHOCOCHO+H 2 O) -417.7134232 0.069508 0.079710 0.080655 0.030783 - R6: (CHOCOCHO) -341.2469850 0.046251 0.052495 0.053439 0.015015 - S9
TS6 P6: (CHOCOCHO) rot R7: ((CH 2 OCOCH 2 O) rot + OH) TS7 P7: ((CHOCOCH 2 O) rot + H 2 O) R8: ((CHOCOCH 2 O) rot + OH) TS8 P8: ((CHOCOCHO) rot +H 2 O) R9: ((CHOCOCHO) rot +OH) TS9 P9: (CHOCO+HCOOH) TS10 P10: (CHOCOOH+CHO) R11: (CHOCOOH+OH) TS11 P11: (CHO+CO 2 +H2O) R12: (CHOCOOH) TS12 P12: (2CO+H 2 O) R13: (CHO+OH) TS13 P13: (CO+H 2 O) -341.2451201-341.247520-418.1785782 (0.754976) -418.1434795 (0.758646) -418.2715683 (0.758754) -417.624354-417.5510674-417.7180519-417.0200546 (0.755629) -417.017809 (0.771481) -417.1048662 (0.755552) -417.0452146 (0.754575) -417.0788229 (0.753279) -378.9592567 (0.754127) -378.9541938 (0.756394) -379.0121602 (0.753033) -303.1828535-303.0707245-303.1669737-189.8354941-189.7257286-189.8167342 0.045681 0.051184 0.052128 0.016159-86.85 0.046049 0.052289 0.053234 0.015395-0.082218 0.090401 0.091345 0.048393-0.079729 0.086363 0.087307 0.048348-909.67 0.079866 0.089818 0.090762 0.042671-0.073053 0.081085 0.082029 0.039452-0.065333 0.073137 0.074081 0.032644-2225.78 0.069204 0.079499 0.080443 0.032348-0.057286 0.066091 0.067036 0.023033-0.056886 0.064827 0.065772 0.023891-285.46 0.060093 0.068825 0.069769 0.022031-0.058768 0.065827 0.066771 0.026868-559.58 0.057384 0.066625 0.067569 0.019651-0.053993 0.061356 0.062301 0.021573-0.050506 0.057043 0.057987 0.018987-1401.02 0.047675 0.059523 0.060467 0.002680-0.042812 0.047703 0.048647 0.014599-0.033656 0.039622 0.040566 0.004426-1208.64 0.032864 0.043676 0.044620-0.010549-0.033577 0.036757 0.037701 0.009493-0.025662 0.029735 0.030680 0.000646-1491.74 0.026922 0.033813 0.034757-0.004449 - S10
Figure S3: Potential energy surface for (a) H-abstraction from C α -OH, (b) Formation and fragmentation of CHOCOCHO, (c) Glycolate Pathway and (d) Formation of CO and CO 2 obtained from DFT calculations. All the labeling of transition states (TS) are in consistent with Figure S1 and S2. (a) H-abstraction from C α -OH;here TS2G represents TS2 of glygolate pathway S11
TS3 TS4 TS5 TS6 TS7 TS8 (c ) Glycolate Pathway (d) Formation of CO and CO 2 S12
Table S6: Activation barrier (E a ), rate constant (k), pre-exponential factor (A), constant n and Wigner constant ((T)) at 298.15 K and 1 atm pressure in TST and TSTW method. The bold font values are for deuterated steps. E a TST TSTW k(/s) A(/s) n Wigner (T) k(/s) A(/s) n H-abstraction from C α -OH 7.4 2.31 10 07 3.37 10 12-0.3 3.88 8.96 10 07 4.45 10 14-1.0 8.8 2.20 10 06 2.87 10 12-0.3 2.52 5.53 10 06 1.39 10 13-0.6 7.5 1.90 10 07 3.84 10 12-0.2 3.88 7.37 10 07 5.06 10 14-0.9 8.6 3.09 10 06 1.04 10 12 0.03 2.52 7.79 10 06 5.07 10 12-0.2 2.8 5.80 10 10 8.24 10 11 0.2 1.00 5.83 10 10 7.76 10 11 0.2 Formation of CHOCOCHO Pathway A 1.5 5.19 10 11 2.37 10 11 0.7 1.22 6.31 10 11 4.30 10 10 0.9 23.3 5.51 10 05 1.56 10 12-0.1 1.87 1.03 10 04 8.62 10 11-0.1 18.1 3.41 10 01 1.90 10 9 1.2 1.51 5.16 10 01 3.65 10 8 1.4 52.4 2.19 10 26 1.11 10 10 1.0 5.84 1.28 10 25 2.12 10 13-0.1 52.7 1.50 10 26 1.78 10 10 1.1 3.76 5.64 10 26 1.87 10 12 0.4 Pathway B 21.4 1.34 10 03 5.36 10 12-0.5 1.96 2.62 10 03 4.08 10 12-0.5 22.3 2.96 10 04 4.25 10 12-0.4 1.59 4.70 10 04 9.89 10 11-0.3 51.6 8.37 10 26 3.57 10 10 0.8 4.81 4.03 10 25 2.06 10 13-0.2 52.5 1.87 10 26 5.18 10 10 0.7 3.15 5.88 10 26 1.45 10 12 0.2 2.2 1.47 10 11 9.11 10 11 0.2 1.01 1.48 10 11 7.54 10 11 0.2 Fragmentation of CHOCOCHO 8.4 4.42 10 06 1.84 10 12-0.3 1.62 7.18 10 06 4.69 10 11-0.2 39.9 3.23 10 17 2.44 10 10 0.3 1.34 4.32 10 17 3.80 10 09 0.5 Glycolate Pathway 53.4 4.17 10 27 6.31 10 09 1.1 6.40 2.67 10 26 2.03 10 13-0.1 54.6 5.28 10 28 1.11 10 10 0.9 4.13 2.18 10 27 2.26 10 12 0.1 9.6 5.72 10 05 8.56 10 13-0.8 1.35 7.74 10 05 1.33 10 13-0.6 33.3 2.23 10 12 1.79 10 12-0.7 1.16 2.59 10 12 4.06 10 11-0.5 8.0 8.34 10 06 3.45 10 12-0.2 3.92 3.27 10 07 4.89 10 14-1.0 9.1 1.40 10 06 1.42 10 12-0.1 2.54 3.54 10 06 7.27 10 12-0.3 3.7 1.30 10 10 2.57 10 12 0.02 1.01 1.31 10 10 2.22 10 12 0.04 53.8 2.28 10 27 3.04 10 09 1.2 6.57 1.50 10 26 1.13 10 13 0.03 54.8 4.12 10 28 4.21 10 09 1.2 4.21 1.74 10 27 9.88 10 11 0.3 Formation of CO and CO 2 9.3 1.02 10 06 2.97 10 13-0.7 3.55 3.62 10 06 2.02 10 15-1.3 10.0 2.77 10 05 6.10 10 13-0.8 2.37 6.5734E05 1.88 10 14-1.0 67.1 3.62 10 37 2.74 10 06 2.6 3.33 1.21 10 36 1.17 10 08 2.0 67.8 1.13 10 37 2.98 10 06 2.6 2.34 2.64 10 37 8.17 10 06 2.4 69.5 7.12 10 39 4.38 10 06 2.5 3.86 2.75 10 38 5.55 10 08 1.8 69.9 3.19 10 39 3.36 10 06 2.6 2.60 8.29 10 39 2.11 10 07 2.3 S13
Figure S4: Sample IRC plot. S14