Autoxidation of α-pinene at High Oxygen Pressure SUPPORTING INFORMATION
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1 Autoxidation of α-pinene at High Oxygen Pressure Ulrich Neuenschwander and Ive Hermans* Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology (ETH Zurich), HCI E123, Wolfgang-Pauli-Str. 10, CH-8093 Zurich SUPPORTING INFORMATION computational results Contents: S.I.2. 1,4-H shift, fate of R (a) -OO- (b) R (c) -OO S.I.3. 1,7-H shift, fate of R (a) -OO- (b) R (c) -OO S.I.4. O-O bond strength of ipr-oo-ipr, reaction (12) S.I.5. O-O bond strength of ipr-oo-ipr-ooh, reaction (12) S.I.6. Alkoxyl addition to C=C double bond, reaction (14) S.I.7. 1,6-H shift, scheme 3 (R2 R3) S.I.8. 1,5-OH shift, scheme 3 (R3 R4) S.I.9. O 2 elimination, scheme 3 (R5 R3) S.I.10. H abstraction, scheme 3 (R5 DHP) S.I.11. C-O cleavage, scheme 3 (R6 PA) S.I.12. Fate of R3, scheme 3 S.I.1
2 1,4-H shift, fate of R (a) -OO- (b) R (c) -OO Ground state C C C O O C H H H H O O H H H H H Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / C C C O O C H H H H O O H H H H H Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / Imaginary frequency (i cm -1 ): Level: UB3LYP/ G(df,pd) S.I.2
3 1,7-H shift, fate of R (a) -OO- (b) R (c) -OO Ground state C C C O O H H C C C H O C H O H H C H H C H C H H H C H H C C H C H H C H H H C H H H Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / C C C O O H H C C C H O C H O H H C H H C H C H H H C H H C C H C H H C H H H C H H H Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / Imaginary frequency (i cm -1 ): Level: UB3LYP/ G(df,pd)//6-31G(d,p) 5d S.I.3
4 O-O bond strength of ipr-oo-ipr, reaction (12) Ground state (ipro ) O C H C H H H C H H H Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / Ground state (ipr-oo-ipr) O O C H C H H H C H H H C H C H H H C H H H Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / Level: UB3LYP/ G(df,pd) S.I.4
5 O-O bond strength of ipr-oo-ipr-ooh, reaction (12) Ground state (ipro ) O C H C H H H C H H H Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / Ground state ( OiPrOOH) O C H C H H C H H H O O H Ground state (ipr-oo-ipr-ooh) O O C H C H H C H H H C H C H H H C H H H O O H Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / Level: UB3LYP/ G(df,pd) S.I.5
6 Alkoxyl addition to C=C double bond, reaction (14) Ground state (alkoxyl part) O C H C H H H C H H H Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / Ground state (olefin part) C C C C C C C C C C H H H H H H H H H H H H H H H H C H C C H C H H C H H H C H O C H C H C C C H H C H H H C H H H H H H H H Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / Imaginary frequency (i cm -1 ): Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / Level: UB3LYP/ G(df,pd)//6-31G(d,p) 5d S.I.6
7 1,6-H shift, scheme 3 (R2 R3) Supplementary Material (ESI) for Physical Chemistry Chemical Physics Ground state C H H O O C H H O C C H H H C H C H H H Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / C H H O O C H H O C C H H H C H C H H H Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / Imaginary frequency (i cm -1 ): Level: UB3LYP/ G(df,pd)//6-31G(d,p) 5d The barrier of this 1,6-H shift (i.e kcal mol -1 ) is similar to the barrier of the reaction depicted below in the frame of isoprene oxidation (i.e kcal mol -1 on B3LYP/6-31+G(d,p) level; Table S4 in ESI; Peeters et al, PCCP, 2009, 11, 5935). They also performed CBS-APNO calculations (ibid.) and the barrier increased to 16.3 kcal mol -1, other CBS-APNO energy barriers were only 1 kcal mol -1 above the DFT value. Thus, a isodesmic correction of 1.5 kcal mol -1 might be applied to DFT-derived 1,6-H shifts. For the herein reported reaction the corrected barrier would then be 14.5 kcal mol -1. The lower barrier might be partially attributed to the stabilizing hyperconjugation of the cyclobutyl group. S.I.7
8 O 2 elimination, scheme 3 (R5 R3) R5 C H C C H C H H C H H H C O C H C H C C C H C H H H C O O H C H H H C H H H H H O O H H H Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / R3 C H C C H C H H C H H H C O C H C H C C C H C H H H C O O H C H H H C H H H H H H H H Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / O 2 O O Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / Level: MPW1B95/ G(3df,3pd)// MPW1B95/6-31+G(d,p) S.I.8
9 H abstraction, scheme 3 (R5 DHP) Supplementary Material (ESI) for Physical Chemistry Chemical Physics Ground state C C C C C C C C C C H H H H H H H H H H H H H H H H O O O C H C O O H C C C C H C H C H C H H H C H H C H H H C H H H C H H C H C C C C C C C C C C H H H H H H H H H H H H H H H H O O O C H C O O H C C C C H C H C H C H H H C H H C H H H C H H H C H H C H Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / Imaginary frequency (i cm -1 ): Level: UB3LYP/ G(df,pd)//6-31G(d,p) 5d S.I.9
10 1,5-OH shift, scheme 3 (R3 R4) Supplementary Material (ESI) for Physical Chemistry Chemical Physics Ground state (olefin part) C H C C H C H H C H H H C O C H C H C C H C H H C H H H C H H H C C C H C H H H C O O H C H H H C H H H H H Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / C H C C H C H H C H H H C O C H C H C C H C H H C H H H C H H H C C C H C H H H C O O H C H H H C H H H H H Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / Imaginary frequency (i cm -1 ): Level: UB3LYP/ G(df,pd)//6-31G(d,p) 5d S.I.10
11 C-O cleavage, scheme 3 (R6 PA) Supplementary Material (ESI) for Physical Chemistry Chemical Physics Ground state (olefin part) C H H H C H H C H C C H C H C H O H O C H H C H C H H Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / C H H H C C H C H C C H C H C H O H O C H H C H C H H Energy (Hartree): ZPE (Hartree): Rotational constants (GHz): / / Imaginary frequency (i cm -1 ): Level: UB3LYP/ G(df,pd)//6-31G(d,p) 5d S.I.11
12 Fate of R3, scheme 3 It is not immediately clear what the fate of the R3 radical exactly is, since it can either (i) add O 2 or (ii) undergo an intramolecular 1,5-OH shift (see Scheme 3 in the paper). Although the O 2 addition is faster than the 1,5-OH shift, the main reaction flux will still proceed through R4. A thorough analysis of the competing fates of the R3 radical is given in the following table. reaction E b A k (1) R3 R kcal mol -1 UB3LYP/ G(df,pd)//UB3LYP/6-31G(d,p) on the full R3 radical s -1 Literature value, with 2 hindered rotations (L. Zhu, J. W. Bozzelli, L. M. Kardos, J. Phys. Chem. A, 2007, 111, 6361) s -1 R3 R5 1 kcal mol Literature value (Supp.inf. of Peeters et al, PCCP, 2009, 11, 5935) M -1 s s -1 (at 1 bar O2) R5 R3 R5 DHP 15.8 kcal mol -1 MPW1B G(3df,3pd)//MPW1B95/6-31+G(d,p) ground state BDE calculation on the R5 model peroxyl-(1,2,2- trimethyl-2-hydroperoxylethoxy)-verbenyl, including Eb of the forward R3 R5 reaction (microscopic reversibility). Calculation procedure calibrated with the experimental value of oxygen addition to allyl (17.1 kcal mol -1, Supp.inf. of Peeters et al, PCCP, 2009, 11, 5935), using a isodesmic correction term of +0.7 kcal mol kcal mol -1 UB3LYP/ G(df,pd)//UB3LYP/6-31G(d,p) on the full R5 radical s -1 (Supp.inf. of Peeters et al, PCCP, 2009, 11, 5935) s M -1 s -1 (I. Hermans, J. Peeters, P. A. Jacobs, J. Org. Chem., 2007, 72, 3057) 2.8 s -1 The quintessence: O 2 addition to R3 is actually fast and reversible. A dynamic equilibrium between the two radicals R3 and R5 is established (equilibrium constant being determined by the R3 R5 and R5 R3 rate constants); both R3 and R5 can further react. The reaction R3 R4 is, however, approximately 10 4 times faster than the competitive reaction R5 DHP. The selectivity of the proposed pathway (i.e. R3 R4), relative to the side-reaction leading to dihydroperoxide (R3 R5 DHP), can be calculated by the ratio of the corresponding pseudo-first-order k (1) values in the table above: In view of the experimental agreement with the proposed reaction model and an anticipated error of 1 to 2 kcal mol -1 on the E b s, it seems reasonable indeed to neglect the reaction R5 DHP. S.I.12
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