Supporting Information. The preference for dual-gold(i) catalysis in the hydro(alkoxylation vs phenoxylation) of alkynes
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1 Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2017 Supporting Information for The preference for dual-gold(i) catalysis in the hydro(alkoxylation vs phenoxylation) of alkynes Èric Casals-Cruañas, a Oscar F. González-Belman, a Pau Besalú-Sala, a David J. Nelson, b and Albert Poater a * Institut de Química Computacional i Catàlisi, Departament de Química, University of Girona, Campus de Montilivi sn, Girona, Catalonia, Spain. Department of Pure & Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL, UK. albert.poater@udg.edu OH 26.0 H 2 O Ph 0.0 OH 17.5 Ph (IPr)Au O (IPr)Au [Au(OH)(IPr)] + Au(IPr) Ph Ph 3.7 I Au(IPr) O II H + [Au(OH 2 )(IPr)] Ph H 2 O 10.6 Ph -2.4 (IPr)Au O Au(IPr) Figure S1. Computed stationary points for the pre-catalytic activation of [{Au(IPr)} 2 (μ-oh)] + to complexes I and II. Gibbs free energies in chloroform solution are given in kcal/mol (recalculated from ref. 56 at P = 1 atm). I + II 3.0
2 TS(III-IV) [Au] Ph Ph III O [Au] Ph O I+II 0.0 [Au] Ph [Au] III 6.4 O Ph IV 15.0 [Au] Ph [Au] IV 0.6 L [Au] O Ph Ph [Au] 9.8 I O Ph [Au] 8.0 [Au(OHPh)(IPr)] V 2.7 [Au(OHPh)(IPr)] -0.8 Ph H Ph O [Au] 3.9 O Ph [Au] Ph H Ph O H [Au(OHPh)(IPr)] I L = PhOH (Phenol assisted pathway) L = Alkyne (Alkyne assisted pathway) O -6.1 Ph Ph [Au] O Ph H [Au] Ph + II VI Product O Ph Ph H Figure S2. Computed stationary points for the dual-gold catalysed hydrophenoxylation using diphenylacetylene as a substrate and phenol as a nucleophile (Gibbs energies in chloroform solution are given in kcal/mol relative to complex I and the neutral [Au(OPh)(IPr)] complex II. [Au] = [Au(IPr)].
3 CH 3 CCCH 3 HOMO LUMO PhCCPh CF 3 CCCF 3 PhCCPh (real catalyst) Figure S3. Frontier molecular orbitals for the cationic π-gold-alkyne complexes I.
4 Figure S4. Molecular structures of the computed transition states corresponding to the monoaurated mechanism for the in silico NHC = IMe system, involving two molecules of phenol and 1,1,1,3,3,3-hexafluorobut-2-yne. Key distances are indicated in Å.
5 NHC NHC NHC NHC I A TS P Au Au Au R Au Ph R R R R C1 C2 C1 C2 C1 C2 R O R Ph O C1 C2 O R H H H Figure S5. Illustration of key distances (in Ǻ) in the structures considered here. Distance 1 (d1): C1... C2 Distance 2 (d2): Au... C1 Distance 3 (d3): Au... C2 Distance 4 (d4): C1... O
6 Table S1. Benchmark for the alcohol nucleophilic attack to π-gold-dimethyl-alkyne species I (Enthaylpy (H) and Gibbs (G) energies in chloroform are given in kcal/mol, A = adduct; TS = transition state; P = product). P 1 atm E Alcohol I A TS P B2PLYP/def2-TZVP// BP86/def2-TZVP H 2 MeOH B2PLYP/def2-TZVP// BP86/def2-TZVP G 2 MeOH B2PLYP-d3/def2-TZVP// BP86/def2-TZVP H 2 MeOH B2PLYP-d3/def2-TZVP// BP86/def2-TZVP G 2 MeOH M06/TZVP// BP86/def2-TZVP H 2 MeOH M06/TZVP// BP86/def2-TZVP G 2 MeOH B2PLYP/def2-TZVP// BP86/SVP H 1 MeOH B2PLYP/def2-TZVP// BP86/SVP G 1 MeOH B2PLYP/def2-TZVP// BP86/SVP H 2 MeOH B2PLYP/def2-TZVP// BP86/SVP G 2 MeOH B2PLYP-d3/def2-TZVP// BP86/SVP H 1 MeOH B2PLYP-d3/def2-TZVP// BP86/SVP G 1 MeOH B2PLYP-d3/def2-TZVP// BP86/SVP H 2 MeOH B2PLYP-d3/def2-TZVP// BP86/SVP G 2 MeOH M06/TZVP//BP86/SVP H 1 MeOH M06/TZVP//BP86/SVP G 1 MeOH M06/TZVP//BP86/SVP H 2 MeOH M06/TZVP//BP86/SVP G 2 MeOH P = 1354 atm E Alcohol I A TS P B2PLYP/def2-TZVP// BP86/def2-TZVP H 2 MeOH B2PLYP/def2-TZVP// BP86/def2-TZVP G 2 MeOH B2PLYP-d3/def2-TZVP// BP86/def2-TZVP H 2 MeOH B2PLYP-d3/def2-TZVP// BP86/def2-TZVP G 2 MeOH M06/TZVP// BP86/def2-TZVP H 2 MeOH M06/TZVP// BP86/def2-TZVP G 2 MeOH B2PLYP/def2-TZVP// BP86/SVP H 1 MeOH B2PLYP/def2-TZVP// BP86/SVP G 1 MeOH B2PLYP/def2-TZVP// BP86/SVP H 2 MeOH B2PLYP/def2-TZVP// BP86/SVP G 2 MeOH B2PLYP-d3/def2-TZVP// BP86/SVP H 1 MeOH B2PLYP-d3/def2-TZVP// BP86/SVP G 1 MeOH B2PLYP-d3/def2-TZVP// BP86/SVP H 2 MeOH B2PLYP-d3/def2-TZVP// BP86/SVP G 2 MeOH M06/TZVP//BP86/SVP H 1 MeOH M06/TZVP//BP86/SVP G 1 MeOH M06/TZVP//BP86/SVP H 2 MeOH M06/TZVP//BP86/SVP G 2 MeOH
7 Table S2. Key distances, in Å, in the structures depicted in Figure 6 (d1 = C1 C2; d2 = Au C1; d3 = Au C2; d4 = C1 O) involved in the nucleophilic attack of η 2 -complex I by the alcohol. Complex A is the adduct formed initially, TS is the transition state for nucleophilic attack, and P is the complex produced. Mayer Bond Orders are provided for C1 C2 (MBO1), Au C1 (MBO2), Au C2 (MBO3), and C1 O (MBO4). Alkyne Alcohol d1 d2 d3 d4 MBO1 MBO2 MBO3 MBO4 I A TS 1 MeOH P A Me TS 2 MeOH P A Me TS 1 PhOH P A TS 2 PhOH P I A TS 1 MeOH P A TS 2 MeOH P A TS 1 PhOH P A TS 2 PhOH P I A TS 1 MeOH P A F F F TS 2 MeOH P A TS F F 1 PhOH P F A TS 2 PhOH P
8 Table S3. Grimme dispersion correction on geometry optimizations (Internal Energy (E), Enthaylpy (H) and Gibbs (G) energies in kcal/mol). Alkyne Alcohol E H G Without dispersion: I CH 3 CCCH A CH 3 CCCH 3 1 MeOH TS CH 3 CCCH 3 1 MeOH P CH 3 CCCH 3 1 MeOH With D3 dispersion: I CH 3 CCCH A CH 3 CCCH 3 1 MeOH TS CH 3 CCCH 3 1 MeOH P CH 3 CCCH 3 1 MeOH With D3bj dispersion: I CH 3 CCCH A CH 3 CCCH 3 1 MeOH TS CH 3 CCCH 3 1 MeOH P CH 3 CCCH 3 1 MeOH
9 Table S4. Alcohol nucleophilic attack to π-gold-alkyne species I (Gibbs energies in chloroform are given in kcal/mol, A = adduct; TS = transition state; P = product). Alkyne Alcohol E H G I CH 3 CCCH A CH 3 CCCH 3 1 MeOH TS CH 3 CCCH 3 1 MeOH P CH 3 CCCH 3 1 MeOH A CH 3 CCCH 3 2 MeOH TS CH 3 CCCH 3 2 MeOH P CH 3 CCCH 3 2 MeOH A CH 3 CCCH 3 1 PhOH TS CH 3 CCCH 3 1 PhOH P CH 3 CCCH 3 1 PhOH A CH 3 CCCH 3 2 PhOH TS CH 3 CCCH 3 2 PhOH P CH 3 CCCH 3 2 PhOH I PhCCPh A PhCCPh 1 MeOH TS PhCCPh 1 MeOH P PhCCPh 1 MeOH A PhCCPh 2 MeOH TS PhCCPh 2 MeOH P PhCCPh 2 MeOH A PhCCPh 1 PhOH TS PhCCPh 1 PhOH P PhCCPh 1 PhOH A PhCCPh 2 PhOH TS PhCCPh 2 PhOH P PhCCPh 2 PhOH I CF 3 CCCF A CF 3 CCCF 3 1 MeOH TS CF 3 CCCF 3 1 MeOH P CF 3 CCCF 3 1 MeOH A CF 3 CCCF 3 2 MeOH TS CF 3 CCCF 3 2 MeOH P CF 3 CCCF 3 2 MeOH A CF 3 CCCF 3 1 PhOH TS CF 3 CCCF 3 1 PhOH P CF 3 CCCF 3 1 PhOH A CF 3 CCCF 3 2 PhOH TS CF 3 CCCF 3 2 PhOH P CF 3 CCCF 3 2 PhOH I HCCH A HCCH 1 MeOH TS HCCH 1 MeOH P HCCH 1 MeOH A HCCH 2 MeOH TS HCCH 2 MeOH P HCCH 2 MeOH A HCCH 1 PhOH TS HCCH 1 PhOH P HCCH 1 PhOH A HCCH 2 PhOH TS HCCH 2 PhOH P HCCH 2 PhOH I FCCF A FCCF 1 MeOH TS FCCF 1 MeOH P FCCF 1 MeOH A FCCF 2 MeOH TS FCCF 2 MeOH P FCCF 2 MeOH A FCCF 1 PhOH TS FCCF 1 PhOH P FCCF 1 PhOH A FCCF 2 PhOH TS FCCF 2 PhOH P FCCF 2 PhOH
10 Table S5. Main distances (d1 = C1 C2; d2 = Au C1; d3 = Au C2; d4 = C1 O; in Ǻ, see Figure S5) involved in the nucleophilic attack of the alcohol to the π-gold-alkyne complex I (A = adduct; TS = transition state; P = product); and the corresponding Mayer Bond Orders (MBO1 = C1 C2; MBO2 = Au C1; MBO3 = Au C2; MBO4 = C1 O; in Ǻ). Alkyne Alcohol d1 d2 d3 d4 MBO1 MBO2 MBO3 MBO4 I CH 3 CCCH A CH 3 CCCH 3 1 MeOH TS CH 3 CCCH 3 1 MeOH P CH 3 CCCH 3 1 MeOH A CH 3 CCCH 3 2 MeOH TS CH 3 CCCH 3 2 MeOH P CH 3 CCCH 3 2 MeOH A CH 3 CCCH 3 1 PhOH TS CH 3 CCCH 3 1 PhOH P CH 3 CCCH 3 1 PhOH A CH 3 CCCH 3 2 PhOH TS CH 3 CCCH 3 2 PhOH P CH 3 CCCH 3 2 PhOH I PhCCPh A PhCCPh 1 MeOH TS PhCCPh 1 MeOH P PhCCPh 1 MeOH A PhCCPh 2 MeOH TS PhCCPh 2 MeOH P PhCCPh 2 MeOH A PhCCPh 1 PhOH TS PhCCPh 1 PhOH P PhCCPh 1 PhOH A PhCCPh 2 PhOH TS PhCCPh 2 PhOH P PhCCPh 2 PhOH I CF 3 CCCF A CF 3 CCCF 3 1 MeOH TS CF 3 CCCF 3 1 MeOH P CF 3 CCCF 3 1 MeOH A CF 3 CCCF 3 2 MeOH TS CF 3 CCCF 3 2 MeOH P CF 3 CCCF 3 2 MeOH A CF 3 CCCF 3 1 PhOH TS CF 3 CCCF 3 1 PhOH P CF 3 CCCF 3 1 PhOH A CF 3 CCCF 3 2 PhOH TS CF 3 CCCF 3 2 PhOH P CF 3 CCCF 3 2 PhOH I HCCH A HCCH 1 MeOH TS HCCH 1 MeOH P HCCH 1 MeOH A HCCH 2 MeOH TS HCCH 2 MeOH P HCCH 2 MeOH A HCCH 1 PhOH TS HCCH 1 PhOH P HCCH 1 PhOH A HCCH 2 PhOH TS HCCH 2 PhOH P HCCH 2 PhOH I FCCF A FCCF 1 MeOH TS FCCF 1 MeOH P FCCF 1 MeOH A FCCF 2 MeOH TS FCCF 2 MeOH P FCCF 2 MeOH A FCCF 1 PhOH TS FCCF 1 PhOH P FCCF 1 PhOH A FCCF 2 PhOH TS FCCF 2 PhOH P FCCF 2 PhOH
11 Table S6. Chemical hardness (η) and electrophilicity (ω) of the intermediate species involved in the alkoxylation (in a.u.; A = Adduct, P = Product). Alkyne Alcohol E HOMO E LUMO η Ω MeOH PhOH I CH 3 CCCH A CH 3 CCCH 3 1 MeOH P CH 3 CCCH 3 1 MeOH A CH 3 CCCH 3 2 MeOH P CH 3 CCCH 3 2 MeOH A CH 3 CCCH 3 1 PhOH P CH 3 CCCH 3 1 PhOH A CH 3 CCCH 3 2 PhOH P CH 3 CCCH 3 2 PhOH I PhCCPh A PhCCPh 1 MeOH P PhCCPh 1 MeOH A PhCCPh 2 MeOH P PhCCPh 2 MeOH A PhCCPh 1 PhOH P PhCCPh 1 PhOH A PhCCPh 2 PhOH P PhCCPh 2 PhOH I CF 3 CCCF A CF 3 CCCF 3 1 MeOH P CF 3 CCCF 3 1 MeOH A CF 3 CCCF 3 2 MeOH P CF 3 CCCF 3 2 MeOH A CF 3 CCCF 3 1 PhOH P CF 3 CCCF 3 1 PhOH A CF 3 CCCF 3 2 PhOH P CF 3 CCCF 3 2 PhOH I HCCH A HCCH 1 MeOH P HCCH 1 MeOH A HCCH 2 MeOH P HCCH 2 MeOH A HCCH 1 PhOH P HCCH 1 PhOH A HCCH 2 PhOH P HCCH 2 PhOH I FCCF A FCCF 1 MeOH P FCCF 1 MeOH A FCCF 2 MeOH P FCCF 2 MeOH A FCCF 1 PhOH P FCCF 1 PhOH A FCCF 2 PhOH P FCCF 2 PhOH
12 Table S7. Natural Bond Order (NBO) charges (in electrons). Alkyne Alcohol Au C1 C2 O I CH 3 CCCH A CH 3 CCCH 3 1 MeOH P CH 3 CCCH 3 1 MeOH A CH 3 CCCH 3 2 MeOH P CH 3 CCCH 3 2 MeOH A CH 3 CCCH 3 1 PhOH P CH 3 CCCH 3 1 PhOH A CH 3 CCCH 3 2 PhOH P CH 3 CCCH 3 2 PhOH I PhCCPh A PhCCPh 1 MeOH P PhCCPh 1 MeOH A PhCCPh 2 MeOH P PhCCPh 2 MeOH A PhCCPh 1 PhOH P PhCCPh 1 PhOH A PhCCPh 2 PhOH P PhCCPh 2 PhOH I CF 3 CCCF A CF 3 CCCF 3 1 MeOH P CF 3 CCCF 3 1 MeOH A CF 3 CCCF 3 2 MeOH P CF 3 CCCF 3 2 MeOH A CF 3 CCCF 3 1 PhOH P CF 3 CCCF 3 1 PhOH A CF 3 CCCF 3 2 PhOH P CF 3 CCCF 3 2 PhOH I HCCH A HCCH 1 MeOH P HCCH 1 MeOH A HCCH 2 MeOH P HCCH 2 MeOH A HCCH 1 PhOH P HCCH 1 PhOH A HCCH 2 PhOH P HCCH 2 PhOH I FCCF A FCCF 1 MeOH P FCCF 1 MeOH A FCCF 2 MeOH P FCCF 2 MeOH A FCCF 1 PhOH P FCCF 1 PhOH A FCCF 2 PhOH P FCCF 2 PhOH
13 Table S8. Nucleophilic attack of the π-gold-alkyne species I by the alcohol. Gibbs energies in chloroform solution are given in kcal/mol, A = adduct; TS = transition state; P = product). Alkyne Alcohol E H G I A TS 1 MeOH P A Me TS 2 MeOH P A Me TS 1 PhOH P A TS 2 PhOH P Alkyne Alcohol E H G I A TS 1 MeOH P A TS 2 MeOH P A TS 1 PhOH P A TS 2 PhOH P Alkyne Alcohol E H G I A TS 1 MeOH P A F F F TS 2 MeOH P A TS F F 1 PhOH P F A TS 2 PhOH P
14 Table S9. Chemical hardness (η) and electrophilicity (ω) of the intermediate species involved in the hydroalkoxylation/hydrophenoxylation reaction (in a.u.). A is the adduct between complex I and the alcohol, and P is the product complex. Alcohol E HOMO E LUMO η ω MeOH PhOH Alkyne Alcohol I A MeOH P Me A MeOH P A Me 1 PhOH P A PhOH P Alkyne Alcohol I A MeOH P A MeOH P A PhOH P A P 2 PhOH Alkyne Alcohol I A MeOH P F F F A MeOH P A PhOH P F F F A PhOH P
15 Table S10. Benchmark for the nucleophilic attack of II to π-gold-dimethyl-alkyne species I (Gibbs (G) energies in chloroform are given in kcal/mol). Geometry optimization Thermal correction E gas G gas (M06/TZVP) E solv G solv (M06/TZVP) E solv (M06/DEF2TZVP) G solv (M06/DEF2TZVP) I+II BP86/SVP BP86/SVP III BP86/SVP BP86/SVP III-IV BP86/SVP BP86/SVP IV BP86/SVP BP86/SVP I+II BP86/Def2TZVP BP86/Def2TZVP III BP86/Def2TZVP BP86/Def2TZVP III-IV BP86/Def2TZVP BP86/Def2TZVP IV BP86/Def2TZVP BP86/Def2TZVP I+II BP86-d3/Def2TZVP BP86-d3/Def2TZVP III BP86-d3/Def2TZVP BP86-d3/Def2TZVP III-IV BP86-d3/Def2TZVP BP86-d3/Def2TZVP IV BP86-d3/Def2TZVP BP86-d3/Def2TZVP I+II BP86-d3/SVP BP86-d3/SVP III BP86-d3/SVP BP86-d3/SVP III-IV BP86-d3/SVP BP86-d3/SVP IV BP86-d3/SVP BP86-d3/SVP I+II BP86/SVP M06/SVP III BP86/SVP M06/SVP III-IV BP86/SVP M06/SVP IV BP86/SVP M06/SVP I+II BP86/TZVP BP86/TZVP III BP86/TZVP BP86/TZVP III-IV BP86/TZVP BP86/TZVP IV BP86/TZVP BP86/TZVP NHC = IPr I+II BP86/SVP BP86/Def2TZVP III BP86/SVP BP86/Def2TZVP III-IV BP86/SVP BP86/Def2TZVP IV BP86/SVP BP86/Def2TZVP NHC = IPr I+II BP86/SVP BP86-d3/Def2TZVP III BP86/SVP BP86-d3/Def2TZVP III-IV BP86/SVP BP86-d3/Def2TZVP IV BP86/SVP BP86-d3/Def2TZVP
16 %V bur calculations By using SambVca (version 2), developed by Cavallo and coworkers, it is possible to analyse and visualise the first coordination sphere around the metal where the catalysis takes place. The buried volume (%V bur ) provides a convenient single number that describes the steric impact of the ligand, and steric maps and per quadrant measures of %V bur provide more information about the way in which the steric bulk is distributed. Splitting %Vbur into quadrant contributions quantifies any asymmetry in the way the ligand wraps around the metal. This analysis shows how the shape of the reactive pocket is modified when moving from IPr to IMe for species gold-alkyne species I. Structure/Activity Relationships of the monogold systems With the mono- and digold-catalysed mechanisms described by DFT calculations, and even though the digold mechanism is found to be strongly favored with respect to the monogold one when the catalyst concentration is relatively not low, the role of each species involved was probed. Structure/activity relationships are important because they determine the scope and limitations of the synthetic methodology. The results are collected in Tables S4 and S8 to allow direct comparisons to be made, including the optimised energy in solvent (E) as well as the enthalpy (H) for the sake of consistency with the work of Belanzoni, Zuccaccia and co-workers. 28 The adduct A is formed from the interaction of η 2 -alkyne complex I with the alcohol, due to the favourable interaction between the carbon atoms of the alkyne and the oxygen of the alcohol, together with hydrogen bonds of the latter atom to hydrogen atoms attached to the alkyne. This interaction is rather weak. In terms of Gibbs free energies, A is more stable than the separated species. Mayer Bond Orders (MBO) for these adducts are collected in Table S5 (vide infra), and demonstrate that the nature of the bond is neither covalent nor ionic because the corresponding MBOs are null. The nucleophilic attack enjoys a reduced barrier if two molecules of alcohol are involved. However, this favourable effect is not that significant in energy terms once the entropic effects are also considered. Kinetically, the upper energy point on the free energy surface is this transition state. The general trends are that electron-withdrawing substituents on
17 the alkyne (such as trifluoromethyl groups) increase the barrier by at least 3-5 kcal/mol, and give barriers up to twice as high as the simple but-2-yne substrate. Alkyl alcohols facilitate the alkoxylation, reducing the barrier by around 10 kcal/mol. The combination of diphenylacetylene and phenol leads to prohibitively large barriers and an intermediate that is very high in energy (both > 30 kcal/mol). The steric properties of the substituents on the alkyne do not play a significant role; the small H and F substituents on acetylene and difluoroacetylene, respectively, lead to completely different behaviour (see Tables S4-S5). Intermediate P, the product of the alkoxylation, is thermodynamically less stable than the initial reactants in all cases except where trifluoromethyl or methyl groups are the substituents on the alkyne. P becomes much more thermodynamically stable when it bears electron withdrawing substituents on the alkyne, while larger substituents lead to less stable P. In general, for monogold-catalysed hydroalkoxylation, alkyl substituents on the alkyne lead to lower barriers (TS) but aryl substituents lead to more thermodynamically stable product complexes P. Notably, this key step of the reaction (from I to P) is not thermodynamically favourable overall unless the alkyne bears highly electron-withdrawing substituents; subsequent protodeauration renders the reaction irreversible. The counterion might compensate for this instability of species P, and even decrease the barrier. However, in the previous study by Zuccaccia and coworkers, 28 such an effect was not included in the calculations. The results from the monogold catalysed pathway can be compared to those from the dual gold-catalysed mechanism. In the latter, the highest energy barrier is 15.0 kcal/mol for the hydrophenoxylation of diphenylacetylene and 8.9 kcal/mol for the hydromethoxylation of but-2-yne. The latter value can be compared to 26.9 and 22.9 kcal/mol for the monogold-catalysed pathway, depending on whether one or two methanol molecules participate. Thus, the monoaurated process is at least 14.0 kcal/mol more expensive. The analysis of the geometry of the transition state (TS) turns out to be fundamental, describing early or late transition states. When the C O distance is close to 1.5 Ǻ which is similar to the C-O bond distance in P, the corresponding TS can be considered a late transition state. This occurs in all the systems studied here except for those based on fluorinated alkynes. Furthermore, when the alkyne has aryl substituents, the TS structures have slightly less late character. On the other hand, when two alcohol molecules are involved, the second alcohol molecule somewhat stabilises the developing
18 positive charge on the alcohol proton, thus dramatically reducing the later transition state character. The character of the carbon-carbon bond in η 2 -alkyne complex I is essentially unaffected once the alcohol bonds to either of the carbon atoms, with a small elongation (< 0.09 Ǻ) in all structures studied. In the corresponding step of the dual gold-catalysed mechanism (see TS(III-IV) in Figures 2 and Figure S2), the C O distance in the transition state is Ǻ (versus Ǻ for the monogold pathway), confirming that the transition state has less late character in the dual gold-catalysed mechanism. For a more detailed analysis of the structural changes during the hydroalkoxylation, Mayer Bond Orders (MBO) of the main distances involved in the C-O bond formation are collected in Table S2. The MBO for the former C-C of the alkyne does not change whereas the Au-C MBOs change dramatically. However, the MBOs for the Au-C bonds span a range from 0.6 to 0.7, and are thus rather far from 1.0 in the initial η 2 -alkyne complex I. As would be expected, one Au-C bond sees an increase in MBO of around 0.2 forming a formal Au-C σ-bond in P while the MBO of the other Au-C bond decreases to 0.1 or lower in P. For the dual gold-catalysed mechanism, in the nucleophilic attack (III to IV) the MBO of the C-C bond decreases from to Thus, a significant difference of is observed, to be compared with and for one or two methanol units, in the monogold-catalysed pathway. Furthermore, the new C-O bond in IV displays a MBO of 0.772, significantly higher than and in the monogold-catalysed pathway (with one or two methanol molecules, respectively). To distinguish between the effects of steric and electronic factors, a natural population analysis has been carried out to evaluate the Natural Bond Orbital (NBO) charges (see Table S7). The charge on the carbon atom in η 2 -complex I or in adduct A would be expected to be slightly positive in order to favour the nucleophilic attack of the alcohol; however, this is not observed and no trend is evident even when fluorinated substrates are considered. There is no trend in the charge on gold. A deeper analysis of the electronic properties was carried out by means of conceptual DFT to discuss the electrophilicity and chemical hardness from the frontier molecular orbitals (Tables S6 and S9). The electrophilicity of the phenol is slightly higher than that of methanol, but more significant differences appear when the different alkynes are evaluated. If there are fluorinated substituents the system is much more electrophilic.
19 Table S10. 3D view and xyz coordinate data sets and absolute energies in a.u. for DFT optimized complexes. 1A (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Au O H Au C N C H C H N C C C H C H C H C C H C H H H C H H H C H C H H H C H H H C C C H C H C H C C H C H H H C H H H C H C H H H C H H H C N C H C H N C C C H C H C H C C H C H H H
20 C H H H C H C H H H C H H H C C C H C H C H C C H C H H H C H H H C H C H H H C H H H
21 MeOH-CH C N C C N C C Au C C O C H H H H H H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
22 MeOH-CHTs C N C C N C C Au C C O C H H H H H H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
23 MeOH-CHProd C C N C N C Au C C C H H H H H H H H O C H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
24 PhOH-CH C N C C N C C Au C C O H H H H H H H H H H H C C C C H C H C H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
25 PhOH-CHTs C N C C N C C Au C C H H H H H H H H H H C C C C C C H H H H H O H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
26 PhOH-CHProd C C N C N C Au C C C H H H H H H H H H H C C C C C C H H H H H O H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
27 MeOH-FC C N C C N C C Au C C O C H H H H H H H H H H H H F F (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
28 MeOH-FCTs C N C C N C C Au C C O C H H H H H H H H H H H H F F (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
29 MeOH-FCProd C C N C N C Au C C C H H H H H H H H O C H H H H F F (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
30 PhOH-FC C N C C N C C Au C C O H H H H H H H H H F F C C C C H C H C H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
31 PhOH-FCTs C N C C N C C Au C C H H H H H H H H C C C C C C H H H H H O H F F (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
32 PhOH-FCProd C C N C N C Au C C C H H H H H H H H C C C C C C H H H H H O H F F (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
33 MeOH-CH-MeOH C N C C N C C Au C C H H H H H H H H H H C H H O H H C H H H O H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
34 MeOH-CHTs-MeOH C N C C N C C Au C C O C H H H H H H H H H H H H H H C H H H O H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
35 MeOH-CHProd-MeOH C N C C N C C Au C C O C H H H H H H H H H H H H H H C H H H O H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
36 PhOH-CH-PhOH C N C C N C C Au C C O H H H H H H H H H H H C C C C H C H C H H H C C C C C C H H H H H O H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
37 PhOH-CHTs-PhOH C N C C N C C Au C C H H H H H H H H H H C C C C C C H H H H H O H C C C C C C H H H H H O H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
38 PhOH-CHProd-PhOH C C N C N C Au C C C H H H H H H H H H H C C C C C C H H H H H O H C C C C C C H H H H H O H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
39 MeOH-FC-MeOH C N C C N C C Au C C O C H H H H H H H H H H H H F F C H H H O H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
40 MeOH-FCTs-MeOH C N C C N C C Au C C O C H H H H H H H H H H H H F F C H H H O H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
41 MeOH-FCProd-MeOH C N C C N C C Au C C O C H H H H H H H H H H H H F F C H H H O H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
42 PhOH-FC-PhOH C N C C N C C Au C C O H H H H H H H H H F F C C C C H C H C H H H C C C C C C H H H H H O H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
43 PhOH-FCTs-PhOH C N C C N C C Au C C H H H H H H H H C C C C C C H H H H H O H F F C C C C C C H H H H H O H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
44 PhOH-FCProd-PhOH C C N C N C Au C C C H H H H H H H H C C C C C C H H H H H O H F F C C C C C C H H H H H O H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
45 MeOH-MeC C N C C N C C Au C C C C O C H H H H H H H H H H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
46 MeOH-MeCTS C N C C N C C Au C C C C O C H H H H H H H H H H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
47 MeOH-MeCprod C C N C N C Au C C C C C H H H H H H H H H H H H H H O H C C C C H C H C H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
48 MeOH-CF 3 C N C C N C C Au C C C C O C H H H H H H H H H H H H F F F F F F (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
49 MeOH-CF 3 prod C C N C N C Au C C C C C H H H H H H H H O C H H H H F F F F F F (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
50 MeOH-PhC C N C C N C C Au C C O C H H H H H H H H H H H H C C C C H C H C H H H C C C C H C H C H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
51 MeOH-PhCTS (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N C C N C C Au C C O C H H H H H H H H H H H H C C C C H C H C H H H C C C C H C H C H H H
52 MeOH-PhCprod (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C C N C N C Au C C C H H H H H H H H O C H H H H C C C C H C H C H H H C C C C H C H C H H H
53 PhOH-CF 3 C N C C N C C Au C C C C O H H H H H H H H H H H H H H H C C C C H C H C H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
54 PhOH-CF 3 TS C N C C N C C Au C O H H H H H H H H H C C C F F F F F F C C C C H C H C H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
55 PhOH-CF 3 prod C C N C N C Au C C C C C H H H H H H H H O H C C C C H C H C H H H F F F F F F (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
56 PhOH-MeC C C N C N C Au C C C C C H H H H H H H H H H H H H H O H C C C C H C H C H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
57 PhOH-PhC (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C C N C N C Au C C C H H H H H H H H O H C C C C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H
58 MeOH-MeC-MeOH C C N C N C Au C C C C C H H H H H H H H H H H H H H O C H H C H H H O H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
59 MeOH-MeCTS-MeOH C C N C N C Au C C C C C H H H H H H H H H H H H H H O C H H C H H H O H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
60 MeOH-MeCprod-MeOH C C N C N C Au C C C C C H H H H H H H H H H H H H H O C H H C H H H O H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
61 MeOH-CF 3 -MeOH C N C C N C C Au C C C C O C H H H H H H H H H H H H O H C H H H F F F F F F (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
62 MeOH-CF 3 TS-MeOH C C N C N C Au C C C C C H H H H H H H H O C H H C H H H O H H H F F F F F F (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
63 MeOH-CF 3 prod-meoh C C N C N C Au C C C C C H H H H H H H H O C H H C H H H O H H H F F F F F F (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
64 MeOH-PhC-MeOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N C C N C C Au C C O C H H H H H H H H H H H H O H C H H H C C C C H C H C H H H C C C C H C H C H H H
65 MeOH-PhCTS-MeOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N C N C Au C C C H H H H H H H H O C H H C H H H O H H H C C C C H C H C H H H C C C C H C H C H H H
66 MeOH-PhCprod-MeOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C C N C N C Au C C C H H H H H H H H O C H H C H H H O H H H C C C C H C H C H H H C C C C H C H C H H H
67 PhOH-MeC-PhOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N C C N C C Au C C O H H H H H H H H H O H C C C C H C H C H H H C C C C H C H C H H H C H H H C H H H
68 PhOH-MeCTS-PhOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C C N C N C Au C C C H H H H H H H H O H O H C C C C H C H C H H H C C C C H C H C H H H C H H H C H H H
69 PhOH-MeCprod-PhOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C C N C N C Au C C C H H H H H H H H O H O H C C C C H C H C H H H C C C C H C H C H H H C H H H C H H H
70 PhOH-CF 3 -PhOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N C C N C C Au C C C C O H H H H H H H H H O H F F F F F F C C C C H C H C H H H C C C C H C H C H H H
71 PhOH-CF 3 TS-PhOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C C N C N C Au C C C H H H H H H H H O H O H C C F F F F F F C C C C H C H C H H H C C C C H C H C H H H
72 PhOH-CF 3 prod-phoh (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C C N C N C Au C C C H H H H H H H H O H O H C C C C H C H C H H H C C C C H C H C H H H C C F F F F F F
73 PhOH-PhC-PhOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N C C N C C Au C C O H H H H H H H H H O H C C C C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H
74 PhOH-PhCTS-PhOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N C C N C C Au C C O H H H H H H H H H O H C C C C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H
75 PhOH-PhCprod-PhOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C C N C N C Au C C C H H H H H H H H O H O H C C C C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H
76 ALCOHOL O C C O C C O C C O C H H H H H H H H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
77 CAT N C C N C C Au C C C C C H H H H H H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
78 CAT+MeOH C N N C C C C H H Au O H C H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
79 CAT+MeO C N N C C C C H H Au C O H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
80 I (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C C N C N C Au C C C C C H H H H H H H H H H H H H H O C H H C H H O C H H C H H C H H C H H C H H H O H O
81 Me-CC-Me C C C C H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
82 MeOH-I C C N C N C Au C C C C C H H H H H H H H H H H H H H O C H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
83 MeOH-I+II C N N C C C C H H Au C C C N N C C C C H H Au C O C C H H H H H H H H H H H H H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
84 MeOH-I+II--IV C N N C C C C H H Au C C C N N C C C C H H Au C O C C H H H H H H H H H H H H H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
85 MeOH-I+MeOH C C N C N C Au C C C C C H H H H H H H H H H H H H H O C H H C H H H O H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
86 MeOH-IV C N N C C C C H H Au C C C N N C C C C H H Au C O C C H H H H H H H H H H H H H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
87 MeOH-IV-VI-ALKYNE (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H Au C C C N N C C C C H H Au C O C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H
88 MeOH-IV-VI-MeOH C N N C C C C H H Au C C C N N C C C C H H Au C O O H C C C H H H H H H H H H H H H H H H H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
89 MeOH-RC C N C C N C C Au C C C C O C H H H H H H H H H H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
90 MeOH-RC-MeOH C N C C N C C Au C C C C O C H H H H H H H H H H H H H H H H H H O H C H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
91 MeOH-TS C N C C N C C Au C C C C O C H H H H H H H H H H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
92 MeOH-TS+MeOH C C N C N C Au C C C C C H H H H H H H H H H H H H H O C H H C H H H O H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
93 MeOH-VII-6-ALKYNE C C C N N C C C C H H Au C O H C C C C C C H H H H H H H H H H H H H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
94 MeOH-VI C O C C C H H H C H H H C N N C C C C H H Au H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
95 MeOH-VII C N N C C C C H H Au C O C C H C C H H H H H H H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
96 MeOH-VI-VII-MeOH C N N C C C C H H Au C O C C C H H H C H H H C N N C C C C H H Au H O C H H H H H H H H H H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
97 MeOH O C H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
98 PhOH C C C C H C H C H H H O H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
99 Ph-CC-Ph C C C C C C H C H C H H H C C C C H C H C H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
100 PRODcis C O C C H C C H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
101 PRODPhcis (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C C C C H C H C H H H O C C C C C H C C H H H C C C C H C H C H H H H C H
102 PRODPhtrans C C C C H C H C H H H O C C C C C H C C H H H C C C C H C H C H H H H C H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
103 PRODtrans C O C C H C C H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
104 RC C N C C N C C Au C C C C O C C O C C O C C O C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
105 REAL-CAT (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C C C C H C H C H H H C C C C H C H C H H H
106 REAL-CAT+PhOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C C H C H C H H H O H
107 REAL-CAT+PhOH+PhCCPh-CAT+Ph (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= O Au C N C H C H N C C C H C H C H C C H C H H H C H H H C H C H H H C H H H C C C H C H C H C C H C H H H C H H H C H C H H H C H H H C C C C H C H C H H H C C C C C C H C H C H H H H C C C C
108 H C H C H H H
109 REAL-CAT+PhO (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C C H C H C H H H O
110 REAL-MeCCMe-MeOH-I (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C O C C H H H H H H H H H H
111 REAL-MeCCMe-MeOH-I+MeOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C O C C H O H C H H H H H H H H H H H H
112 REAL-MeCCMe-MeOH-RC+MeOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C O C C H O H C H H H H H H H H H H H H
113 REAL-MeOH-I (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C O C C C C H C H C H H H C C C C H C H C H H H H H H H
114 REAL-MeOH-I+MeOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C O C C C C H C H C H H H C C C C H C H C H H H H O H C
115 H H H H H H
116 REAL-MeOH-RC (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C O C C C C H C H C H H H C C C C H C H C H H H H H H H
117 REAL-MeOH-RC+MeOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C O C C C C H C H C H H H C C C C H C H C H H H H O H C
118 H H H H H H
119 REAL-MeOH-TS+MeOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C O C C C C H C H C H H H C C C C H C H C H H H H O H C
120 H H H H H H
121 REAL-PhOH-I+II (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C N N C C C C H H C C C C C C H H H C C C C C C C H H H
122 C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C C H C H C H H H O C C C C H C H C H H H C C C C H C H C H H H
123 REAL-PhOH-I+II--IVcis (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C N N C C C C H H C C C C C C H H H C C C C C C C H H H
124 C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C C H C H C H H H O C C C C H C H C H H H C C C C H C H C H H H
125 REAL-PhOH-I+II-IV (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C N N C C C C H H C C C C C C H H H C C C C C C C H H H
126 C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C C H C H C H H H O C C C C H C H C H H H C C C C H C H C H H H
127 REAL-PhOH-I+PhOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C O C C C C H C H C H H H C C C C H C H C H H H H O H C C
128 C C H C H C H H H C C C C H C H C H H H
129 REAL-PhOH-IVcis (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C N N C C C C H H C C C C C C H H H C C C C C C C H H H
130 C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C C H C H C H H H O C C C C H C H C H H H C C C C H C H C H H H
131 REAL-PhOH-I (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C O C C C C H C H C H H H C C C C H C H C H H H H C C C C
132 H C H C H H H
133 REAL-PhOH-IV (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C N N C C C C H H C C C C C C H H H C C C C C C C H H H
134 C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C C H C H C H H H O C C C C H C H C H H H C C C C H C H C H H H
135 REAL-PhOH-IV-VI-ALKYNE (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C N N C C C C H H C C C C C C H H H C C C C C C C H H H
136 C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C C H C H C H H H O C C C C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H C C C C C C H C H C H H H
137 REAL-PhOH-IV-VI-PhOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C N N C C C C H H C C C C C C H H H C C C C C C C H H H
138 C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C C H C H C H H H O O H C C C C H C H C H H H C C C C H C H C H H H C C C C H C H C H H H
139 REAL-PhOH-VII-6-ALKYNE (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C C C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C C H C H C H H H O H C C C C H C H C H H H C C C C
140 H C H C H H H C C C C H C H C H H H C C C C C C H C H C H H H
141 REAL-PhOH-VII-6-PhOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C C H C H C H H H O C C H O H C C C C H C H C H H H C C
142 C C H C H C H H H C C C C H C H C H H H
143 REAL-PhOH-VII (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C C H C H C H H H O C C H C C C C H C H C H H H C C C C
144 H C H C H H H
145 REAL-PhOH-VI-VII-PhOH (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C C H C H C H H H O C C C H H H C H H H C N N C C C C H
146 H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au H O C C C C H C H C H H H
147 REAL-PhOH-VI (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C N N C C C C H H C C C C C C H H H C C C C C C C H H H C H C C H C C H C C H C C H H H H H H H H H H H H H H H H H H H H H H H H Au C C C C C C H C H C H H H O C C C C H C H C H H H C C C C H
148 C H C H H H
149 TS C N C C N C C Au C C C C O C C O C C O C C O C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=
The Innocent role of Sc 3+ on Non-Heme Fe catalyst in O 2 environment
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