Supplementary Information. Fenton s Reagent Catalysed Release of Carbon Monooxide from 1,3- Dihydroxy Acetone

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1 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 , India. b Department of Chemistry, Sir Parashurambhau College, Pune , 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/ G(d,p) methodology and in aqueous phase with dielectric constant 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) ( ) TS ( ) P1: (CH 2 OCOCH 2 OH+H 2 O) ( ) R2: (CH 2 OCOCH 2 OH+OH) ( ) TS ( ) P2: (CH 2 OCOCH 2 O+H 2 O) ( ) Pathway_a R3: (CH 2 OCOCH 2 O) ( ) TS ( ) P3: (CH 2 OCOCH 2 O) rot ( ) R4:((CH 2 OCOCH 2 O) rot +OH) ( ) TS ( ) P4: ((CHOCOCH 2 O) rot +H 2 O) ( ) R5: ((CHOCOCH 2 O) rot +OH) TS P5: ((CHOCOCHO) rot +H 2 O) S1

2 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) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) Pathway_b S2

3 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/ G(d,p) methodology and in aqueous phase with dielectric constant for Glycolate Pathway. Species Energy Imag (<S 2 ZPE E H G >) (Hz) R1: (CH 2 OHCOCH 2 OH+OH) ( ) TS ( ) P1: (CH 2 OCOCH 2 OH+H 2 O) ( ) R2: (CH 2 OCOCH 2 OH) ( ) TS ( ) P2: (CH 2 OCOCH 2 OH) rot ( ) R3: ((CH 2 OCOCH 2 OH) rot +OH) TS P3: (CHOCOCH 2 OH+H 2 O) R4: (CHOCOCH 2 OH +OH) ( ) TS ( ) P4: (HCOOH+COCH 2 OH) ( ) TS ( ) P5: (CH 2 OHCOOH+CHO) ( ) R6: (CH 2 OHCOOH +OH) ( ) TS ( ) P6: (CH 2 OCOOH +H 2 O) ( ) R7: (CH 2 OCOOH) ( ) TS ( ) P7: (CH 2 OCOOH)rot ( ) R8: (CH 2 OCOOH rot +OH) TS S3

4 P8: (CHOCOOH+H 2 O) 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

5 R6 TS6 P6 R7 TS7 P7 R8 TS8 P8 R9 TS9 P9 R10 (P9) TS10 P10 R11 TS11 P11 S5

6 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

7 R5 (P4) TS5 P5 R6 TS6 P6 R7 TS7 P7 R8 TS8 P8 Table S3: Energies calculated at CCSD(T)//M06 2X/ G(d, p) level of theory in atomic units and in aqueous phase with dielectric constant 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) TS P1: (CH 2 OCOCH 2 OH+H 2 O) R2: (CH 2 OCOCH 2 OH+OH) TS P2: (CH 2 OCOCH 2 O+H 2 O) R3: (CH 2 OCOCH 2 O) TS P3: (CH 2 OCOCH 2 O) rot R4:((CH 2 OCOCH 2 O) rot +OH) TS S7

8 P4: ((CHOCOCH 2 O) rot +H 2 O) R5: ((CHOCOCH 2 O) rot +OH) TS P5: ((CHOCOCHO) rot +H 2 O) R6: (CH 2 OCOCH 2 O+OH) TS P6: (CHOCOCH 2 O+H 2 O) R7: (CHOCOCH 2 O+OH) TS P7: (CHOCOCHO+H 2 O) R8: (CHOCOCHO) TS P8: (CHOCOCHO) rot R9: ((CHOCOCHO) rot +OH) TS P9: (CHOCO+HCOOH) TS P10: (CHOCOOH+CHO) R11: (CHOCOOH+OH) TS P11: (CHO+CO 2 +H2O) R12: (CHOCOOH) TS P12: (2CO+H 2 O) R13: (CHO+OH) TS P13: (CO+H 2 O) Table S4: Energies calculated at CCSD(T)/ G(d, p)//m06 2X/ G(d, p) level of theory in atomic units and in aqueous phase with dielectric constant for Glycolate Pathway. Species CCSD(T) R1: (CH 2 OHCOCH 2 OH+OH) TS P1: (CH 2 OCOCH 2 OH+H 2 O) R2: (CH 2 OCOCH 2 OH) TS P2: (CH 2 OCOCH 2 OH) rot R3: ((CH 2 OCOCH 2 OH) rot +OH) TS P3: (CHOCOCH 2 OH+H 2 O) R4: (CHOCOCH 2 OH +OH) TS P4: (HCOOH+COCH 2 OH) TS P5: (CH 2 OHCOOH+CHO) S8

9 R6: (CH 2 OHCOOH +OH) TS P6: (CH 2 OCOOH +H 2 O) R7: (CH 2 OCOOH) TS P7: (CH 2 OCOOH)rot R8: (CH 2 OCOOH rot +OH) TS P8: (CHOCOOH+H 2 O) 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/ G(d,p) methodology and in aqueous phase with dielectric constant 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) ( ) TS ( ) P1: (CH 2 OCOCH 2 OH+H 2 O) ( ) R2: (CH 2 OCOCH 2 OH+OH) ( ) TS ( ) P2: (CH 2 OCOCH 2 O+H 2 O) ( ) R3: (CH 2 OCOCH 2 O) ( ) TS ( ) P3: (CH 2 OCOCH 2 O) rot ( ) R4: (CH 2 OCOCH 2 O+OH) ( ) TS ( ) P4: (CHOCOCH 2 O+H 2 O) ( ) R5: (CHOCOCH 2 O+OH) TS P5: (CHOCOCHO+H 2 O) R6: (CHOCOCHO) S9

10 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) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) S10

11 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

12 TS3 TS4 TS5 TS6 TS7 TS8 (c ) Glycolate Pathway (d) Formation of CO and CO 2 S12

13 Table S6: Activation barrier (E a ), rate constant (k), pre-exponential factor (A), constant n and Wigner constant ((T)) at 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 Formation of CHOCOCHO Pathway A Pathway B Fragmentation of CHOCOCHO Glycolate Pathway Formation of CO and CO E S13

14 Figure S4: Sample IRC plot. S14