This is the submitted version of the journal article: Moya, Alicia; Creus, Jordi; Romero Fernández, Nuria; [et al.]. «Organocatalytic vs. Ru-based electrochemical hydrogenation of nitrobenzene in competition with the hydrogen evolution reaction». Dalton transactions, Vol. 49, Issue 19 (May 2020), p. 6446-6456. DOI 10.1039/D0DT01075H This version is available at https://ddd.uab.cat/record/281243 under the terms of the license Page 1 of 223 Dalton Transactions Guidelines for Referees Thank you very much for agreeing to review this manuscript for Dalton Transactions. Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. 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Please do not Dalton adjust margins Transactions Page 8 of 223 ARTICLE Organocatalytic vs Ru-based Electrochemical Hydrogenation of Nitrobenzene in Competition with Hydrogen Evolution Reaction Received 00th January 20xx, Alicia Moya,a Jordi Creus,b,c Nuria Romero,b José Alemán,d,e Xavier Solans-Monfort,b Karine Accepted 00th January 20xx Philippot,c Jordi García-Antón,b Xavier Sala,*b and Rubén Mas-Ballesté*a,e DOI: 10.1039/x0xx00000x The electrochemical reduction of organic contaminants allows its removal from water. In this contribution, the electrocatalytic hydrogenation of nitrobenzene is studied using both oxidized carbon fibres and ruthenium nanoparticles supported on unmodified carbon fibres as catalysts. The two systems produce azoxynitrobenzene as main product, while aniline is only observed in minor quantities. Although PhNO2 hydrogenation is the favoured reaction, the hydrogen evolution reaction (HER) competes in both systems under the catalytic conditions. The H2 formation occurs in larger amounts when using the Ru nanoparticle based catalyst. While similar reaction outputs have been observed for both catalytic systems, DFT calculations revealed some significant differences related to distinct interactions between the catalytic material and the organic substrates or products, which could pave the way for the design of new catalytic materials. Metal-free catalysts, such as carbon-based materials16,17 as well Introduction as Ru-based catalysts18–20 seem to be ideal alternatives for this purpose. Electrochemical reduction of organic substrates is an important In a recent report, we explored carbon microfibres (CFs) synthetic method but also, an efficient way to remove prepared by the pyrolysis of polyacrylonitrile (PAN) as an persistent pollutants1–3 and to produce energy vectors based on alternative electro-organocatalytic material for HER (Fig. 1a, reversible hydrogenation/dehydrogenation processes.4–6 Such top).21 CFs with a graphene-like structure including pyridyl processes, when carried out in the presence of proton sources, moieties can be easily oxidized to generate carboxylic acid require electrocatalysts able to hydrogenate organic groups at the surface, constituting nicotinic fragments in the its functionalities.7 Such electrocatalytic materials are intended to structure. The resulting material that will be further referred as increase the activity and selectivity of the reduction reaction. ox-CF presents high HER electrocatalytic activity. Indeed, ox-CF Regarding the selectivity, the occurrence of Hydrogen Evolution acts as catalytic centres for the HER in a way similar to those of Reaction (HER) as a parasite process in competition with the NADPH in biological systems22,23 and Hantzsch esters in hydrogenation of organic reagents is ubiquitously observed.8 synthetic reduction procedures.24–26 In another work, we used The characteristics of the electrocatalytic materials will have pristine CFs as support for Ru-NPs in order to achieve stable and enormous influence on the reaction output, tipping the balance high surface area functionalized electrodes (Fig. 1a, bottom).27 in favour of one or another process. Thus, a deep understanding Our results demonstrated the viability of such hybrid material of the mechanism underlaying both pathways will enable to composed by Ru-NPs onto CFs as remarkable electrocatalysts rationally design electrocatalytic materials capable to for the HER (referred as Ru-CF). A common feature of both hydrogenate organic substrates or to mediate HER. Indeed, a systems (ox-CF and Ru-CF) is the generation of hydride species wide range of materials has been already studied due to the that can be protonated to form molecular hydrogen. need of clean and renewable alternatives to the use of fossil Additionally, they could hydrogenate a variety of substrates, fuels.9–11 Although Pt-based catalysts are known to be highly widening the applicability of electrochemical systems usually performant for HER, its substitution by cheaper and employed for HER. Remarkably, such electrocatalytic earth-abundant catalytic materials is highly demanded.12–15 procedures are convenient strategies that avoid the manipulation of H2 gas or metal hydride derivatives (LiAlH4 or a. Department of Inorganic Chemistry (module 07).Universidad Autónoma de Madrid, NaBH4), commonly used in chemical hydrogenation processes. 28049, Madrid, Spain. E-mail: ruben.mas@uam.es b. Departament of Chemistry. Universitat Autònoma de Barcelona, 08193, In this work, we have compared the electrocatalytic HER and Cerdanyola del Vallès, Barcelona, Spain. E-mail: Xavier.sala@uab.cat the hydrogenation of nitrobenzene (PhNO2) as model substrate, c. CNRS, LCC (Laboratoire de Chimie de Coordination), UPR8241, Université de using modified carbon fibres (ox-CF and Ru-CF) as Toulouse, UPS, INPT, F-31077 Toulouse cedex 4, France. d. Department of Organic Chemistry (module 01). Universidad Autónoma de Madrid, electrocatalytic materials (see Fig. 1b). The reduction of PhNO2 28049, Madrid, Spain. is of great interest since nitro aromatic compounds (such as e. Institute for Advanced Research in Chemical Sciences (IAdChem), Universidad Autónoma de Madrid, 28049, Madrid, Spain. explosives, dyes, agrochemicals or pesticides) are common † Electronic Supplementary Information (ESI) available. See water contaminants.28,29 Although many alternatives have been DOI: 10.1039/x0xx00000x Please do not adjust margins Page 9 of 223 Please do not Dalton adjust margins Transactions ARTICLE Journal Name explored,30–35 electrochemical procedures are still the most Experimental convenient ways to reduce PhNO2 and related compounds. Materials However, in the presence of protic media, this process would typically be in competition with HER. Again, platinum electrode All reagents, solvents and materials were purchased from is often used for electrochemical reduction of nitrobenzene,36– commercial sources and used without further purification. 38 limiting their applicability for large scale processes.39 Thus, Specifically, fabric of carbon fibre (Twill 2x2 3K weight 200 g/m2 there is a need to find efficient, inexpensive, easy to make and width 1200 mm, Model HA2301) was purchased from recyclable electrocatalytic materials free of noble metals40,41 for ClipCarbono. the reduction of nitroaryl compounds. This reaction will be deeply presented in this manuscript, considering HER as a Electrode Preparation competitive process. We will determine the intrinsic properties The commercial carbon fibre is prepared in a 6 cm long bunch of ox-CF and Ru-CF as electrocatalysts for both reactions of fibres. Then, it is joined to a copper wire and tight with a (compare Fig. 1b top and bottom) by means of combination of Teflon tape. The hand-made electrodes are modified using two experimental and theoretical results. This work will provide different approaches, namely: 1) oxidative treatment of the fundamental understandings on the distinctive catalytic carbon fibre and 2) ex-situ deposition of Ru-NPs. For the behaviour of metal-based and metal-free electrocatalysts. The oxidized CF brushes, they are treated 30 minutes with sulfuric obtained fundamental insights can pave the way for the future acid (98%) at room temperature with stirring and later they are design of active and selective electrocatalytic materials for HER immersed into a mixture 1:1 of H2SO4/H2O2. The mixture should or hydrogenation of organic substrates. be freshly prepared to obtain its stronger oxidative potential and thus, be able to oxidize the carbon fibre. Finally, the electrodes are washed and sonicated in distilled water to neutralize its surface, later washed in ethanol and dried with a heat gun. Characterization of this material was previously reported and confirms that the oxidation process changes the chemical features of the CF surface (generation of carboxylic groups, transforming pyridinic fragments into nicotinic ones) whereas keep its bulk properties and morphology.21 For the Ru- based CF, 2 cm of CF electrodes were soaked overnight in a THF (10 mL) crude dispersion of RuPP NPs27,42 inside a Fisher-Porter bottle under an Ar atmosphere. Then, the supernatant was removed through cannula and the resulting CF materials were rinsed with pentane (3x10 mL) and dried under vacuum. RuPP@pCF. TEM: Ø = 1.8 ± 0.3 nm. ICP(Ru%): 0.47%. Electrochemistry Electrochemical experiments were performed under an argon atmosphere at room temperature in CH3CN. Sodium perchlorate (NaClO4) was used as supporting electrolytes. Measurements were carried out using an Ivium CompaqStat potentiostat interfaced with a computer. A standard three- electrode electrochemical cell was used with Ag/AgCl reference electrode. The working electrode was carbon fibre brush: pristine, oxidized and modified with inorganic nanoparticles. The counter electrode was a pristine carbon fibre brush. Gas Chromatography The evolution of the nitrobenzene during the electrocatalytic reaction was monitored by gas chromatography, by injecting samples of the intern atmosphere to an Agilent 7820A GC system equipped with a mass spectroscopy detector (5977B MSD). For gas chromatography quantification of nitrobenzene Fig. 1 Schematic representation of a) Carbon Fibre-based electrocatalysts for HER and its derivatives, the solvent of the working electrode solution (previous work)21,27 and b) HER vs hydrogenation of PhNO2 using same electrocatalysts (this work). is reduced at low pressure and then it is solved with 1 mL of CHCl3 which is able to solve the nitrobenzene and its derivatives but not the inorganic salt of the electrolyte. An aliquot of 0.2 mL of the solution is mixed with 0.2 mL of methylnaphthalene as 2 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx Please do not adjust margins Please do not Dalton adjust margins Transactions Page 10 of 223 Journal Name ARTICLE standard. A calibrate of nitrobenzene, nitrosobenzene, Results and discussion azoxynitrobenzene, diphenylazobenzene and aniline was Experimental Results carried out enabling the quantification of the products. Details on synthesis and characterization of the electrocatalytic materials used in this comparative study are reported Computational Details elsewhere.21,27 Previous mechanistic studies revealed that both, Quantum chemistry calculations were carried out using the ox-CF and Ru-CF, generate hydrides that after protonation, lead density functional theory (DFT). For the organocatalytic system, to HER. Herein, we studied if these systems are capable to geometry optimizations were performed using the M06-2X transfer the hydride to the organic substrate: PhNO2. Although functional43 in combination with the 6-311G** basis set.44 For the product typically formed from this process is simply aniline, comparison some selected PBE-D2 calculations were also several other species can be generated. Therefore, as previously carried out for this system (see S.I.).46,48 Solvent effects were reported, a more complex mechanism should be considered for included with the solvation model density (SMD)45 and hydrogenation of nitrobenzene (see Fig. 2).56 considering acetonitrile (ε= 37.5) as solvent. Graphitic surface The electrochemical behaviour of nitrobenzene has been was modelled using a fragment composed by 4 fused aromatic analysed by cyclic voltammetry (Fig. S1). A reduction signal is rings (1 pyridine + 3 benzenes) as a compromise between observed at E1/2= -1.1 V vs Ag/AgCl, which is associated to a performance and computational cost a carboxylic group in the reversible electron transfer process. According to this result, -1 meta position versus pyridine nitrogen. All optimizations were V vs Ag/AgCl was chosen as the limit potential for all performed without any geometrical constraint and harmonic electrochemical experiments in order to achieve vibrational frequencies were used to characterize minima and electrocatalytic hydrogenation and avoid electrochemical transition states in the potential energy surface. Transition electron transfer. The choice of an adequate proton source is states were connected to products by optimization of determinant for the efficiency of the reaction. Also, in order to geometries slightly modified from the transition states. All the understand such effect, some factors have to be considered: 1) calculations were performed using the Gaussian09 program.46 Electrocatalytic hydrogenation of nitrobenzene will compete For modelling the reactivity with Ru-NPs, we used the PBE47 with HER and 2) Hydride regeneration on the catalytic centres functional as implemented in the VASP code.48,49 Grimme (D2) involves injection of two electrons into the electrocatalytic empirical correction was added to account for dispersion material and further protonation. Combination of both factors interactions.50 The core electrons were described by ultrasoft will determine the effect of the proton source in the output of pseudopotential51,52 and the external ones by plane wave basis the electrocatalytic PhNO2 hydrogenation. In order to optimize set, with a kinetic energy cutoff of 500 eV. With the aim of the composition of our systems, we have compared linear minimizing replica interactions, a cubic cell of 25 Å was sweep voltammetry results of ox-CF and Ru-CF using water (1 employed. The k point grid includes the  point only, as a M), trifluoroacetic acid (TFA, 20 mM) and a mixture of both as consequence of the discrete nature of the system. The energy proton sources (Fig. S2) in acetonitrile. Maximized convergence criteria were fixed to 10–5 and 10–4 eV for electrochemical response is observed for both catalytic systems electronic and geometry relaxations, respectively. Solvent when a mixture of water and TFA is used. Fig. 3 presents the effects were included during the optimization with the implicit linear sweep voltammetries recorded in the absence (top) and continuum model implemented in VASPsol53 and using in the presence (bottom) of nitrobenzene at a scan rate of 10 acetonitrile as solvent (ε= 37.5). Transition states were located by using climbing image nudged elastic band (CI-NEB) method Nitrosobenzene N-phenylhydroxylamine Aniline O OH without including solvent effects.54,55 Six or eight images per N HN NH2 NEB were used. The highest in energy image was used for locating the final transition state by performing a gas-phase geometry optimization with the quasi-Newton algorithm (1) (2) (3) implemented in VASP. Convergence was considered to be achieved when forces were smaller than 0.02 eV/Å. Solvent Azoxynitrobenzene Diphenyldiazene Diphenylhydrazine effects at transition state were included with a single-point calculation at the optimizes structure. For the case of the hydronium ion, the transition state was located by performing N N VASPsol restricted optimizations, in which the O-H distance of O NH N N HN hydronium was fixed in each step. The highest in energy point was used as starting point for localizing the transition state. The energies reported along the text are all given in kcal mol-1. (4) (5) (6) Fig. 2 Possible species that can be generated from hydrogenation of nitrobenzene with species detected in this work highlighted inside the frames. This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 3 Please do not adjust margins Page 11 of 223 Please do not Dalton adjust margins Transactions ARTICLE Journal Name cannot be uniquely related to the intrinsic properties of the active sites but also to their relative concentration on the electrode surface. Furthermore, we investigated the reaction output after a longer reaction time (5 vs 15 h, Fig. 4a and 4b). After 15 h, the consumption of nitrobenzene is almost complete for both electrocatalytic materials. The pristine carbon fibre electrode was also tested for 15 h. In these conditions, no significant amounts of products were found, corroborating that the catalytic behaviour observed with the two other materials results from either the oxidation of carbon fibres or the presence of Ru-NPs (Fig. S3). As shown on Fig. 4 and S4, regardless of the reaction time (5 or 15 h), the major product of the nitrobenzene reduction after bulk electrolysis at -1 V is azoxynitrobenzene dimeric species (4). In addition, residual amounts of aniline (3) and diphenyldiazene (5) are also observed. Interestingly, amounts of aniline (3) at 15 h are equal or even lower than those detected at 5 h. In contrast, the amounts of azoxynitrobeneze (4) and diazobenzene (5) are significantly superior at 15 h than at 5 h. These observations indicate that, a) the generation of Fig. 3 Linear sweep voltammetries measured using pristine (solid line), oxidized (dashed aniline (3) corresponds to short reaction times, b) the formation line) and Ru-based (dotted line) carbon fibre electrodes in the absence (top) and in the of dimeric species (4 and 5) needs accumulation of monomeric presence (bottom) of 10 mM of nitrobenzene. In all cases, solvent is acetonitrile species produced over the electrochemical process, thus containing H2O (1 M), TFA (20 mM) and NaClO4 (0.2 M). requiring longer reaction times. Remarkably, although the nature of the two catalytic systems studied is very distinct, mV/s. Measurements were performed in acetonitrile using similar product compositions are observed. However, faradaic NaClO4 (0.2 M) and TFA (20 mM) and water (1 M) mixture. yields after 15 h electrolysis are approximately 75% for ox-CF The current intensity values at -1 V vs Ag/AgCl are presented and 65% for Ru-CF, thus indicating that HER is the minor process in Table 1. Electrochemical responses of the two materials (ox- but it is more significant for Ru-CF, in agreement with CF and Ru-CF) are much higher than that of the pristine fibre voltammetry data (see Fig. 3). (CF), which demonstrates their catalytic properties, either for the proton reduction or for the nitrobenzene hydrogenation (see -2.48 vs -6.76 and -5.77 mA; -4.85 vs -17.89 and -9.31 mA). Current intensity is greatly enhanced upon addition of PhNO2 when using ox-CF (see -6.76 vs -17.89 mA). However, such an effect is less pronounced for the Ru-CF (see -5.77 vs -9.31 mA). PhNO2 hydrogenation is clearly facilitated with the purely organic electrocatalyst while larger competition between the nitrobenzene hydrogenation and the HER seems to take place when using the inorganic catalyst. With the aim of determining the amount and nature of the final product, a 5 h electrolysis was performed at a constant potential of -1 V vs Ag/AgCl for the two electrocatalysts in the presence of water and TFA mixture (Fig. S3). The reaction outputs have been analysed by gas chromatography (GC). As expected from the current observed in the LSV, higher conversion was found for oxidized carbon fibres (Fig. 4a).It is important to note that the concentration of active sites is difficult to determine accurately. Thus, the activity observed Table 1 Current intensities at -1 V vs Ag/AgCl in 1 M H2O + 20 mM TGA corresponding to the linear sweep voltammetries of Fig. 3. [PhNO2] I of CF I of ox-CF I of Ru-CF (mM) (mA) (mA) (mA) Fig. 4 Reaction products of the electrocatalytic reduction of nitrobenzene at -1 V vs Ag/AgCl after a) 5 h and b) 15 h of reaction using ox-CF and Ru-CF as electrodes in a 0 -2.48 -6.76 -5.77 mixed solution of 1 M of water and 20 mM of TFA in NaClO4 (0.2 M, acetonitrile). 10 -4.85 -17.89 -9.31 4 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx Please do not adjust margins Please do not Dalton adjust margins Transactions Page 12 of 223 Journal Name ARTICLE Theoretical Calculations Methodological Strategies. In order to get a deep understanding of the processes occurring in the electrocatalysis, we performed a computational DFT study. Two sets of calculations were carried out. The full catalytic process involving the organocatalytic system (ox-CF) was represented with a molecular model from a previous work.21 The hybrid Fig.5 Ru57H88 model used for representing the Ru-NPs. M062X functional43 was used and atoms were represented with the 6-311G** basis sets44 including solvation effects of acetonitrile (ε= 37.5) by means of solvation model density pyridinic nitrogen atom and results in its barrierless (SMD).45 The protonation steps of the PhNO2 hydrogenation protonation. Thus, we considered as the starting point the were studied also at this level of theory without including any negatively charged species shown in Scheme 1 (centre) that of the two catalysts in the calculations. The reactivity of Ru-NPs contains a protonated pyridinic nitrogen atom. Further was studied with VASP.48,49 For saving computational time, the evolution of this reduced species consists in its protonation in exploration was limited to the thermodynamics of all steps and the para-position with respect to the nitrogen atom. The the transition states that appeared to be key for the corresponding species can transfer the hydride that is organocatalytic system. VASP includes periodic boundary responsible for the observed reactivity. Taking into account the conditions and defines the basis set with plane wave. Thus, nature of the reaction medium, we have considered two interaction with neighbour images was avoided by using a 25 Å possible protonation agents: TFA molecule and hydrated proton edge cubic unit cell. These calculations were performed with modelled as [H3O(H2O)3]+ according to previous report.59 Very the PBE GGA functional47 and an energy cut-off of 500 eV. similar results have been found using both species, being Dispersion forces were taken into account with Grimme D2 slightly more favourable the protonation with TFA (∆G= -20.9 empirical correction50 (see Computational Details section for kcal mol-1; ∆G‡= 2.9 kcal mol-1) than with [H3O(H2O)3]+ (∆G= - further information). Remarkably, values for the Ru-NPs do not 16.4 kcal mol-1; ∆G‡= 5.3 kcal mol-1). include thermal corrections. However, since all steps are In order to study the processes mediated by Ru-NPs, we unimolecular, ΔE and ΔG values calculated for ox-CF system used a model that includes 57 ruthenium (44 at the surface) and using M062X and PBE-D2 functionals show little variations, 88 hydrogen atoms (Ru57H88, Fig. 5). We have considered this except for the HER, where H2 is formed (see details in S.I.). In structure as a good representation of the active species any case, it is worth to note that since the methodologies used generated under reductive potentials in acidic media, able to for modelling the two catalytic processes differ significantly, we act as an efficient hydride transfer agent. The model choice and have performed some selected calculation with PBE-D2 for the the number of hydrogen atoms is based on Comas-Vives et al. ox-CF system. Results are reported in the S.I. and show the PBE- results.60 Their work showed that a) this model is a good D2 underestimates the energy barriers as it is well-known in the compromise between accuracy and computational cost and b) literature.57 Thus, comparison should be made with caution. the number of hydrogen atoms per surface ruthenium is close Initial Considerations. As reported previously,21 the electro- to the double of surface ruthenium atoms in pristine organocatalytic behaviour of ox-CF is initiated by the injection nanoparticles. of two electrons on the carbon material that contains randomly Hydride Transfer to PhNO2 vs Hydride Protonation. Once the distributed nicotinic fragments. It is known that the value for active species able to perform hydride transfer processes are the work function of highly orientated pyrolytic graphite generated, two potential reactions can take place: hydride (HOPG) in air is c.a. 4.8 eV,58 which is expected to be close to transfer to nitrobenzene and HER. Fig. 6 shows the comparison that of the carbon fibre material. Thus, it should allow of the kinetics and thermodynamics of these processes in stabilization of injected electrons through the graphitic π- presence of model systems for a) ox-CF and b) Ru-CF. Fig. 7 electron density. However, considering the reduced size of the shows some optimized structures. molecular model used in our calculations to simulate the Regarding the reactivity in presence of the ox-CF, graphenic region, the stabilization energy after injection of two calculations show that the hydride transfer to PhNO2 is slightly electrons (3.13 eV) is underestimated. After injection of two endergonic (G= +3.6 kcal mol-1) but this is clearly compensated electrons, the negative charge increases the basicity of the by the subsequent protonation of PhNO2H, which leads to PhNO (1) and a water molecule (origin of the exergonicity; G= -108.9 F3CCOO- kcal mol-1). The competitive H2 formation is also (H2O)3 - G = 2.9 G = 5.3 H thermodynamically favourable both from TFA and hydronium H HOOC HOOC HOOC type molecule [H3O(H2O)3]+, obtaining computed G values of - {(H2O)3H}+ N F3CCOOH N 12.4 and -6.2 kcal mol-1, respectively. From a kinetic point of N H H H view, the hydride transfer to PhNO2 is favoured with respect to G = -16.4 G = -20.9 HER by at least 9.2, kcal mol-1. HER reaction is more favourable Scheme 1 Generation of the species able to transfer hydrides in the ox-CF organo- when TFA is used as proton source. These results are in catalytic system (energy values are given in kcal mol-1). accordance with the high faradaic yields found for nitrobenzene reduction (see above). This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 5 Please do not adjust margins Page 13 of 223 Please do not Dalton adjust margins Transactions ARTICLE Journal Name favourable for nitrobenzene and TFA than for hydronium ion [H3O(H2O)3]+ (see S.I. for further details). Remarkably, two adsorption isoenergetic modes are found for nitrobenzene: a parallel adsorption mainly controlled by dispersion forces and a perpendicular one mainly controlled by the Ru···O interactions (see S.I. for further details). However, only the perpendicular orientation can account for the observed process. As found for the carbon fibres, the hydride transfer to the adsorbed nitrobenzene is slightly unfavourable (E= 4.3 kcal mol-1), but the high exothermicity of the protonation step makes the formation of PhNO + H2O largely favourable. The energy barrier for the hydride transfer to the adsorbed PhNO2 species is computed to be 10.8 kcal mol-1, thus suggesting it is kinetically easy. The hydride protonation in presence of Ru-NPs is easier when involving TFA than [(H3O)(H2O)3]+. The energy barrier is computed to be 17.1 kcal mol-1 from adsorbed TFA. This value is higher than that computed for the PhNO2 hydride transfer. The energy difference between the two processes is slightly smaller than for the ox-CF, indicating that HER (which is in both cases kinetically less favoured) could be a better competing reaction when using Ru-CF rather than when using ox-CF. Fig. 6 Comparison of energetics for the hydride transfer to PhNO2 (black line) and HER Similar conclusions can be inferred from PBE-D2 calculations on (grey lines) using a) ox-CF and b) Ru-CF electrocatalytic models. Hydride protonation can be carried out by TFA (solid grey line) or by [(H3O)(H2O)3]+ (dashed grey line). the organic system. These results agree with the experimentally Energies are given in kcal mol-1. measured faradaic yields for both systems. A potential explanation of the large difference between the HER energy Nitrobenzene hydrogenation and H2 formation on Ru-NPs barriers when involving TFA and [(H3O)(H2O)3]3+ could derive start with the adsorption of the reacting substrates to the from the nature and the strength of the substrate-Ru-NP nanoparticle surface (Table S2). This adsorption is more interaction. Indeed, the Ru···O interaction increases the acidity of TFA favouring the hydride protonation. From PhNO (1) to PhNH2 (3). Evolution of PhNO species formed from the first hydrogenation process (hydride transfer + protonation) to aniline consists of two consecutive hydrogenation steps (Scheme 2). Every hydrogenation step has been considered as an initial hydride transfer with a non- negligible energy barrier, followed by the protonation process, which is generally very favourable, mainly barrier-less and does Fig. 7 Optimized structures found for PhNO2 hydrogenation and HER using TFA and hydronium ion as source of protons: a) transition states shown in Figure 6a for ox-CF model system and b) the starting materials, transition states and final products using Scheme 2 Catalytic evolution of PhNO (1) consisting in two consecutive hydrogenation Ru-CF as catalytic model system as shown in Figure 6b. Cl atom (green) has been added and protonation steps: a) forming hydroxyaniline (2) and b) aniline (3). Energy values to balance charge in periodic calculations. Distances are given in Å. are given in kcal mol-1. 6 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx Please do not adjust margins Please do not Dalton adjust margins Transactions Page 14 of 223 Journal Name ARTICLE Scheme 4 Dimerization processes towards formation of azoxynitrobenzene (4) and azobenzene (5) (energy values are given in kcal mol-1). Scheme 3 Catalytic evolution of Ph-NO to aniline through two successive formation from the reaction of nitrosobenzene (1) and hydrogenation/protonation steps with Ru-NPs. Energies in kcal mol-1 hydroxyaniline (2) intermediates. Effectively, condensation of such compounds is highly favoured, as it should be expected for not involve the electrocatalyst. The hydride transfer to PhNO (1) the formation of a water molecule, which serves as an efficient results in deprotonated hydroxyaniline. This process is driving force of the process (Scheme 4). Thus, while exergonic in presence of ox-CF by -11.7 kcal mol-1. Moreover, hydroxyaniline (2) is slowly being generated, it efficiently reacts the energy barrier is low (G‡= 12.6 kcal mol-1), which indicates with the excess of nitrosobenzene (1) to generate the main final that the process is kinetically favourable (Scheme 2a). In product of this electrocatalytic system, azoxynitrobenzene (4). addition, the protonation of deprotonated hydroxyaniline is Furthermore, formation of the diazo compound (5) that has also very favourable, suggesting that once PhNO (1) is formed, been detected in residual amounts can be explained by the it easily evolves to PhNHOH (2). dimerization of two hydroxyaniline (2) molecules (Scheme 4). Calculations for the second hydrogenation step indicate that Considering that during the reaction, hydroxyaniline (2) coexists hydride transfer to the OH group of hydroxyaniline to generate with an excess on nitrosobenzene (1), this alternative process is a water molecule and deprotonated aniline is very exergonic (- less probable in agreement with the residual amounts of such 36.1 kcal mol-1, Scheme 2b). In this case, transition state has not species experimentally detected. Finally, condensation of been located, indicating that this reaction is barrierless or aniline and nitrosobenzene (1) could also account for the proceeds through a very shallow barrier. Further protonation of formation of the diazo compound (5), which could be deprotonated aniline is very favourable. Consequently, responsible for the disappearance over time of aniline (3). nitrobenzene hydrogenation (Fig. 6) seems to be the rate- Summarising, dimerization processes require significant determining step. Once PhNO (1) is generated, its reduction to concentrations of monomeric species. Therefore, at short aniline (3) should consecutively occur. reaction times, when concentration of products is still low, With the aim of analysing if these two steps are also direct formation of aniline is plausible through the three straightforward in presence of Ru-NPs, we computed the consecutive hydrogenation steps presented above. However, corresponding reaction energies. Results are reported in after longer times of electrolysis, concentration of products Scheme 3 and show that PhNO (1) hydrogenation is similar to increases, and dimeric structures can appear through that found for the ox-CF and it is favourable by -14.9 kcal mol-1. exothermic condensations. Thus, the amounts of aniline On the other hand, the hydrogenation of PhNHOH shows larger experimentally found have been firstly formed (Fig. 4) whereas differences. The resulting products are the same for the two dimeric products have been furtherly produced. The fact that catalytic systems. However, the strong Ru-NPs-H2O interaction the major product found is the azoxynitrobenzene (4) species, and the Ru-PhNH makes the reaction even more exothermic indicates that its hydrogenation is unfavourable as is (E= -50.3 kcal mol-1). The ability of Ru-NPs to coordinate the demonstrated in the next section. reacting substrates changes the thermodynamics in comparison Evaluation of possible evolution of azoxynitrobenzene (4). The with the ox-CF system. In any case, the initial PhNO2 hydride transfer to azoxynitrobenzene (4) and to the other hydrogenation to PhNO (1) appears to be the more challenging dimeric species (diphenyldiazene (5) and diphenylhidrazine (6)) step also when using Ru-NPs (Fig. 6b). involving the two catalytic systems are summarized in Schemes Overall, calculations suggest that aniline (3) should be easily 5 and 6. With ox-CF, the hydride transfer to azoxynitrobenzene formed with the two catalytic systems. However, according to (4) (Scheme 5a) is endergonic (G=+8.1 kcal mol-1) and the the experimental data, aniline (3) is only a minor product computed Gibbs energy barrier is G‡= 22.1 kcal mol-1. These detected in the reaction outcome. Justification of this values indicate that the process is both kinetically and observation is found in the next section. thermodynamically challenging and comparable with the first Dimerization process. The major product observed in the hydride transfer step. This suggests that azoxynitrobenzene (4) electrolysis experiments (see Experimental Results section would hardly be hydrogenated, even though protonation of the above) is the dimeric compound azoxynitrobenzene (4). resulting product to form a water molecule and the diazo Therefore, we decided to evaluate the thermodynamics of its compound is highly exergonic. Therefore, it agrees with the fact This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 7 Please do not adjust margins Page 15 of 223 Please do not Dalton adjust margins Transactions ARTICLE Journal Name Scheme 6 Azoxynitrobenzene conversion to aniline through three successive hydrogenation/protonation steps with Ru-NPs. Energies in kcal mol-1 organocatalytic system, has also been calculated. Fig. 8 shows the optimized structures of azoxynitrobenzene (4), diphenyldiazene (5) and the transition state connecting these two intermediates. The hydrogenation pathways found for azoxynitrobenzene (4) using Ru-CF are significantly different than those calculated Scheme 5 Catalytic evolution of hydrogenation of azoxynitrobenzene towards a) the for ox-CF. The resulting products (PhNNPh + Ru-NPs-OH) using diazo compound, b) the diphenyl hydrazine product and c) aniline (energy values are Ru-CF are the consequence of the formation of a Ru-OH bond given in kcal mol-1). at the nanoparticle surface. Remarkably, despite the large exothermicity of the reaction (E= - 31.9 kcal mol-1), the that azoxynitrobenzene (4) is the major product of computed energy barrier is high (+24.9 kcal mol-1) due to the nitrobenzene hydrogenation. In addition, the small portions of large electronic reorganization to favour the concerted diazo compound observed experimentally are likely formed by formation/cleavage of the Ru···O and N···O bonds. Moreover, the dimerization processes. the two subsequent hydrogenation steps are The potential formation of aniline from the diazo compound thermodynamically favourable (Scheme 6), indicating that (5) in presence of ox-CF has also been considered (Scheme 5b aniline formation from azoxynitrobenzene (4) is and 5c). The obtained results indicate that under the reaction thermodynamically feasible. However, as in the case of ox-CF, conditions, diphenyldiazene (5) would easily evolve to this is not expected to be the main route for aniline formation. diphenylhidrazine (6). Finally, the hydride transfer to this This is due to the large energy barrier of the hydride transfer to hydrazine derivative (6) intermediate leading to aniline azoxynitrobenzene (4), which should be the major dimeric formation is very endergonic (G= + 26.5 kcal mol-1) and species, as found experimentally. kinetically hampered (G‡= 30.5 kcal mol-1, Scheme 5c). Summarizing, calculations on the evolution of Therefore, although further protonation is calculated to be very azoxynitrobenzene (4) suggest that this species could hardly be exothermic, hydrogenation of diphenylhidrazine (6) does not seem the path for the formation of aniline (3). Indeed, the observed aniline is expected to be formed by successive hydrogenation of PhNO2 without dimerization, while the major dimeric product is azoxynitrobenzene (4), which presents a high hydride transfer Gibbs energy barrier. The reactivity of azoxynitrobenzene (4) with the Ru-CF has also been explored, considering the thermodynamics of the Fig, 8 Optimized structures for azoxynitrobenzene intermediate adsorbed on H88Ru57 three potential hydrogenation steps (Scheme 6a to 6c). nanoparticle, the diphenyldiazene resulting from its hydrogenation and the transition Furthermore, the transition state for the hydride transfer to state connecting them. Distances in Å and energies in kcal mol-1 azoxynitrobenzene (4), which appeared to be a key step in the 8 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx Please do not adjust margins Please do not Dalton adjust margins Transactions Page 16 of 223 Journal Name ARTICLE PhNH(OH) to PhNH2) are highly favoured. In parallel to aniline formation, dimeric azoxynitrobenzene compound is generated as a consequence of the highly favourable condensation of PhNO and PhNH(OH). Overall, this work presents an in-depth understanding of the catalytic behaviour of an organic- and a metal-based material that have been previously used as electrocatalysts for HER. Furthermore, we have shown the efficient competition between hydrogenation of PhNO2 with HER. Thus, the methodology reported herein can be applied to the electrochemical remediation of an important class of pollutants Scheme 7 General scheme for the nitrobenzene reduction reaction proposed for the (nitro aryl compounds). In a more general perspective, these two electrocatalytic approaches studied. insights may contribute to the future designs of more efficient catalytic systems for hydrogen production, electrochemical reduced regardless the nature of the electrocatalyst. Thus, waste-water treatments or use of despite the different reactivity expected for ox-CF and Ru-CF, hydrogenation/dehydrogenation based energetic vectors. the chemical identity of the final products should not vary, being azoxynitrobenzene (4) the major product. Overall, our calculations show a reaction mechanism for the Conflicts of interest nitrobenzene hydrogenation that is consistent with the There are no conflicts to declare. experimental data. Despite the different reactivities observed for the two electrocatalysts for some particular steps, the mechanisms for the two systems share the main general issues, Acknowledgements which are summarized in Scheme 7. First, nitrobenzene is This work was supported by Spanish Ministerio de Economia y hydrogenated following a first 2-electron and 2 proton transfer Competitividad (MINECO) (CTQ2015-64261-R, CTQ2017-89132- steps leading to the formation of nitrosobenzene (1), which is P and RTI2018-095038-B-I00), and the Generalitat de Catalunya converted to hydroxyaniline (2) following a further 2-electron (2017SGR1323). We acknowledge the generous allocation of and 2 protons reduction. While this species is being formed, two computer time at the Centro de Computación Científica at the processes can occur: a) further hydrogenation until aniline Universidad Autónoma de Madrid (CCC-UAM) and the Consorci product (3) (detected in low amounts) or b) condensation with de Serveis Universitaris de Catalunya (CSUC). “Comunidad de nitrosobenzene (1) to produce azoxynitrobenzene (4) (observed Madrid” and European Structural Funds (S2018/NMT-4367) are as main product). This dimeric species can hardly be further also acknowledged. J.G.-A. acknowledges Serra Húnter Program reduced, appearing as the final product. In addition, residual and KP CNRS. amounts of diazo compound (5) found in the reaction outcome seems to be the result of dimerization of residual amounts of hydroxyaniline (2). Controversially, according to our theoretical Notes and references data, diazo species (5) should be easily reduced to hydrazine 1 S. Ahmed, M. G. Rasul, R. Brown and M. A. Hashib, J. Environ. compound, which should accumulate because its further Manage., 2011, 92, 311–330. reduction is unfavourable. However, the known high reactivity 2 U. I. Gaya and A. H. Abdullah, J. Photochem. Photobiol. C of hydrazine compounds can account for its further evolution Photochem. Rev., 2008, 9, 1–12. being impossible its detection under the working conditions. 3 W.-D. Oh, Z. Dong and T.-T. Lim, Appl. Catal. B Environ., 2016, 194, 169–201. 4 G. Liang, L. He, H. Cheng, W. Li, X. Li, C. 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Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx Please do not adjust margins Dalton Transactions Page 18 of 223 179x260mm (96 x 96 DPI) Page 19 of 223 Dalton Transactions SUPPORTING INFORMATION Organocatalytic vs Ru-based Electrochemical Hydrogenation of Nitrobenzene in Competition with Hydrogen Evolution Reaction Alicia Moya,a Jordi Creus,b,c Nuria Romero,b José Alemán,d,e Xavier Solans-Monfort,b Karine Philippot,c Jordi García Antón,b Xavier Sala,*b and Rubén Mas-Ballesté*a aDepartment of Inorganic Chemistr (module 07). Universidad Autónoma de Madrid, 28049 Madrid (Spain). E-mail: ruben.mas@uam.es bDepartment of Chemistry, Univeritat Autònoma de Barcelona, 08193, Cerdanyola del Vallès, Barcelona, Spain. E-mail: xavier.sala@uab.cat cCNRS, LCC (Laboratoire de Chimie de Coordination), UPR8241, Université de Toulouse, UPS, INPT, F-31077, Toulouse cedex 4, France. dDepartment of Organic Chemistry (module 01). Universidad Autónoma de Madrid, 28049 Madrid (Spain). eInstitute for Advanced Research in Chemical Sciences (IAdChem). Universidad Autónoma de Madrid, 28049 Madrid (Spain). E-mail: ruben.mas@uam.es fDepartment of Inorganic Chemistry (module 07). Universidad Autónoma de Madrid, 28049 Madrid (Spain). 1 Dalton Transactions Page 20 of 223 Index 1. Experimental Results..........................................................................................................3 1.1. Electrochemical Data........................................................................................................3 1.2. Chromatography Data......................................................................................................5 2. Computational Details .......................................................................................................6 2.2. Adsorption Energies of Reagents on H88Ru57 NPs ...........................................................6 2.2. Comparative Energy Data of ox-CF and Ru-CF catalyst models .....................................7 2.3. M062X optimized geometries associated with the Organic Catalyst: ox-CF.................12 2.3.1. Hydride generation .................................................................................................12 2.3.2. Hydrogen Evolution Reaction..................................................................................21 2.3.3. Hydride transfer processes .....................................................................................33 2.3.4. Thermodynamic assessment of dimerization processes.........................................67 2.3.5. Thermodynamic assessment of protonation steps………………………………………….….73 2.4. PBE-D2 optimized geometries associated with the Organic Catalyst: ox-CF…………….82 2.4.1. Hydrogen Evolution Reaction ...............................................................................82 2.4.2. Hydride transfer processes...................................................................................94 2.5. PBE-D2 optimized geometries associated with the Inorganic Catalyst: Ru-CF ...........106 2.5.1. Adsorption energies of the different reagents .....................................................106 2.5.2. Hydrogen Evolution Reaction................................................................................118 2.5.3. Hydride transfer processes ..................................................................................142 2 Page 21 of 223 Dalton Transactions 1. Experimental Results 1.1. Electrochemical Data 30 6 20 4 10 2 0 0 -10 -2 I (A) I (A) -20 -4 -30 -6 -40 -8 -50 -10 -60 -12 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 Ewe vs Ag/AgCl (V) Ewe vs Ag/AgCl (V) Fig. S1 Cyclic voltammetry of 10 mM of nitrobenzene at a scan rate of 50 mV/s and potential windows of -1.5 – 0 V (left) and -1 V – 0 V (right). Fig. S2 Linear voltammetry measured using pristine (black), oxidised (red) and Ru-based (blue) carbon fibre electrodes in the absence (top) and in the presence (bottom) of 10 mM of nitrobenzene using as electrolyte: 0.2 M of NaClO4 in CH3CN with different proton sources: 1 M of H2O (left), 20 mM of TFA (middle) and their mixture (right). 3 Dalton Transactions Page 22 of 223 Table S1. Current intensities at -1 V vs Ag/AgCl corresponding to the linear sweep voltammetries of Fig. S2. [PhNO2] I of CF (mA) I of ox-CF (mA) I of Ru-CF (mA) Proton Source (mM) 1 M H2O -1.72 -6.13 -4.08 0 20 mM TFA -2.08 -4,92 -6.53 1 M H2O + 20 mM TFA -2.48 -6.76 -5.77 1 M H2O -2.53 -7.14 -9.24 10 20 mM TFA -2.05 -8.93 -6.78 1 M H2O + 20 mM TFA -4.85 -17.89 -9.31 Fig. S3 Comparison of the electrocatalyst for the nitrobenzene conversion a) during 5 h electrolysis in solutions of 1 M of water, 20 mM of TFA and the mixture of both proton source and b) during electrolysis at 5- and 15-hour reaction using 1 M of water and 20 mM of TFA as proton source. 4 Page 23 of 223 Dalton Transactions 1.2. Chromatography Data Fig. S4 Gas chromatograms of electrocatalytic nitrobenzene reduction using pristine carbon fibre (black curve), oxidised carbon fibre (red cure) and Ru-modified carbon fibre (green curve). 5 Dalton Transactions Page 24 of 223 2. Computational Details 2.1. Adsorption Energies of Reagents on H88Ru57 NPs Table S2. Adsorption energies (in kcal·mol-1) of the different reagents on the H88Ru57 nanoparticle model. Species Eads PhNO2 (perpendicular) -10.5 PhNO2 (parallel) -10.6 CH3COOH -9.0 (H3O)(H2O)3Cl -3.3 PhNO -18.0 PhNHOH -8.4 PhNONPh -10.8 PhNNPh -11.1 PhNHNHPh -8.8 6 Page 25 of 223 Dalton Transactions 2.2. Comparative Energy Data of ox-CF and Ru-CF catalyst models Table S3 Electronic energies (in kcal·mol-1) of the hydride transfer to PhNO2 using ox-CF as catalyst. M062X ∆G 0.0 Ea= +23.5 +3.6 ∆E 0.0 Ea= +25.5 +5.7 PBE-D2 ∆G 0.0 Ea= +7.0 +0.6 ∆E 0.0 Ea= +8.7 +1.0 Table S4 Electronic energies (in kcal·mol-1) of the catalytic hydride transfer to PhNO2 using Ru-CF catalyst model. ∆E 0.0 Ea= +10.8 +4.3 7 Dalton Transactions Page 26 of 223 Table S5 Electronic energies (in kcal·mol-1) of the catalytic hydride transfer to TFA using ox-CF catalyst model. M062X ∆G 0.0 Ea= +31.2 -12.4 ∆E 0.0 Ea= +38.7 -3.9 PBE-D2 ∆G 0.0 Ea= +19.2 -18.3 ∆E 0.0 Ea= +23.7 -10.7 Table S6 Electronic energies (in kcal·mol-1) of the catalytic hydride transfer to TFA using Ru-CF catalyst model. ∆E 0.0 Ea= +17.0 +7.3 8 Page 27 of 223 Dalton Transactions Table S7 Electronic energies (in kcal·mol-1) of the catalytic hydride transfer to [(H3O)(H2O)3]+ using ox-CF catalyst model. M062X ∆G 0.0 Ea= +35.1 -6.2 ∆E 0.0 Ea= +40.1 +0.7 PBE-D2 ∆G 0.0 Ea= +19.2 -6.0 ∆E 0.0 Ea= +23.7 -0.3 Table S8 Electronic energies (in kcal·mol-1) of the catalytic hydride transfer to [(H3O)(H2O)3]+ using Ru-CF catalyst model. ∆E 0.0 Ea= +24.9 +1.5 Fig. S5 Catalytic hydrogenation of PhNO using ox-CF (M062X). Energy values are in kcal·mol-1. 9 Dalton Transactions Page 28 of 223 Fig. S6 Catalytic hydrogenation of PhNO using Ru-CF. Energy values are in kcal·mol-1. Table S9 Electronic energies (in kcal·mol-1) of the catalytic hydrogenation of azoxynitrobenzene using ox-CF catalyst model. M062X ∆G 0.0 Ea= +22.1 +8.1 ∆E 0.0 Ea= +23.2 +8.1 PBE-D2 ∆G 0.0 Ea= +6.7 +0.8 ∆E 0.0 Ea= +8.2 +0.5 Table S10 Electronic energies (in kcal·mol-1) of the catalytic hydrogenation of azoxynitrobenzene using Ru-CF catalyst model. ∆E 0.0 Ea= +24.9 -31.9 10 Page 29 of 223 Dalton Transactions Fig. S7 Catalytic hydrogenation of PhNONPh using ox-CF (M062X). Energy values are in kcal·mol-1. Fig. S8 Catalytic hydrogenation of PhNONPh using Ru-CF. Energy values are in kcal·mol-1. 11 Dalton Transactions Page 30 of 223 2.3. M062X optimized geometries associated with the Organic Catalyst: ox-CF 2.3.1. Hydride generation Charge = 0 Multiplicity = 1 Sum of electronic and thermal Free Energies= -1126.899548 6 -3.593226000 -0.344978000 -1.561621000 6 -2.595785000 -1.302848000 -1.658548000 6 -1.250303000 -0.972080000 -1.327393000 6 -0.953892000 0.357371000 -0.866327000 6 -2.009493000 1.331717000 -0.753872000 6 -3.338805000 0.947485000 -1.112017000 6 -0.188081000 -1.888391000 -1.428716000 6 0.393117000 0.705778000 -0.529587000 6 1.449916000 -0.266175000 -0.613273000 6 1.118998000 -1.533745000 -1.088456000 6 2.807565000 0.190953000 -0.194265000 6 2.974853000 1.500925000 0.169501000 6 0.642336000 2.032713000 -0.093979000 6 -1.692267000 2.619636000 -0.285161000 1 -2.479405000 3.358399000 -0.184978000 1 -0.392738000 -2.893767000 -1.780345000 1 -4.610827000 -0.614058000 -1.832913000 1 -2.819883000 -2.307898000 -1.997698000 1 -4.130562000 1.686677000 -1.060340000 1 1.891555000 -2.281924000 -1.189906000 1 3.949283000 1.871548000 0.462140000 6 4.011287000 -0.610169000 -0.075692000 8 5.124730000 -0.186982000 0.216218000 8 3.837642000 -1.928485000 -0.296617000 1 4.698415000 -2.358711000 -0.180157000 7 1.979618000 2.388054000 0.204788000 1 2.172335000 3.338174000 0.491523000 1 -0.135066000 3.960957000 0.372634000 8 0.028101000 -1.427358000 1.887076000 1 -0.363687000 -0.479335000 2.131687000 1 -0.798205000 -2.038326000 1.658089000 1 0.577844000 -1.337464000 1.082355000 8 -1.070542000 0.719546000 2.473224000 1 -0.821376000 1.465711000 1.907556000 12 Page 31 of 223 Dalton Transactions 1 -1.996439000 0.496722000 2.235194000 8 -2.030431000 -2.712436000 1.372533000 1 -2.689958000 -1.990374000 1.453661000 1 -2.249558000 -3.357019000 2.056539000 8 -3.416583000 -0.375309000 1.644698000 1 -3.598648000 0.004258000 0.763646000 1 -4.243915000 -0.313826000 2.136727000 6 -0.376194000 2.958818000 0.030075000 13 Dalton Transactions Page 32 of 223 (Transition state) Charge = 0 Multiplicity = 1 Sum of electronic and thermal Free Energies= -1126.891048 6 -3.715892000 -0.327183000 -1.426875000 6 -2.667241000 -1.246456000 -1.636284000 6 -1.351147000 -0.896780000 -1.354460000 6 -1.075593000 0.399892000 -0.796257000 6 -2.140672000 1.335993000 -0.613762000 6 -3.473996000 0.932294000 -0.933476000 6 -0.234512000 -1.766340000 -1.638984000 6 0.263483000 0.754856000 -0.463751000 6 1.322268000 -0.262111000 -0.487551000 6 1.032629000 -1.430619000 -1.272673000 6 2.709565000 0.279465000 -0.277426000 6 2.875769000 1.587927000 0.051654000 6 0.511561000 2.064913000 -0.047229000 6 -1.837996000 2.623688000 -0.129027000 1 -2.638591000 3.339420000 0.019705000 1 -0.430865000 -2.705343000 -2.144373000 1 -4.732676000 -0.621659000 -1.667248000 1 -2.878481000 -2.227454000 -2.047712000 1 -4.282350000 1.641142000 -0.789615000 1 1.840978000 -2.114843000 -1.498915000 1 3.861158000 1.992016000 0.248637000 6 3.914647000 -0.527318000 -0.186732000 8 5.061317000 -0.105377000 -0.122635000 8 3.676513000 -1.853490000 -0.140928000 1 4.530901000 -2.304921000 -0.063424000 7 1.848552000 2.449957000 0.203088000 1 2.039886000 3.414466000 0.433379000 1 -0.285527000 3.988796000 0.457777000 8 0.551116000 -1.303114000 1.804298000 1 0.031854000 -0.543371000 2.196031000 1 -0.132836000 -2.006293000 1.592561000 1 0.956020000 -0.891462000 0.770262000 8 -1.037349000 0.639601000 2.620212000 1 -0.930309000 1.433656000 2.080222000 1 -1.872145000 0.232209000 2.316099000 14 Page 33 of 223 Dalton Transactions 8 -1.409732000 -2.946229000 1.230398000 1 -2.139835000 -2.308256000 1.351157000 1 -1.548238000 -3.622406000 1.903684000 8 -3.157985000 -0.857681000 1.702704000 1 -3.547543000 -0.475893000 0.900967000 1 -3.894788000 -0.999163000 2.309006000 6 -0.525791000 2.984439000 0.122465000 Charge = 0 Multiplicity = 1 Sum of electronic and thermal Free Energies= -1126.925658 6 -3.242834000 -0.964495000 -1.719604000 6 -2.138469000 -1.837865000 -1.595427000 6 -0.910754000 -1.373256000 -1.181258000 6 -0.752882000 0.012377000 -0.864393000 6 -1.838688000 0.900892000 -1.072175000 6 -3.094415000 0.377058000 -1.480212000 6 0.287262000 -2.213028000 -1.186007000 6 0.506212000 0.500641000 -0.432778000 6 1.577196000 -0.473822000 0.040672000 6 1.455966000 -1.789137000 -0.699704000 6 2.940467000 0.196849000 -0.025737000 6 3.044082000 1.547343000 -0.060262000 6 0.698618000 1.867081000 -0.383040000 6 -1.621317000 2.292276000 -0.896540000 1 -2.448521000 2.979470000 -1.039658000 1 0.204911000 -3.192754000 -1.646870000 1 -4.202402000 -1.359426000 -2.032849000 1 -2.251632000 -2.886542000 -1.850359000 1 -3.925384000 1.062487000 -1.616248000 1 2.329609000 -2.425420000 -0.756139000 1 4.009562000 2.035241000 -0.007959000 6 4.189707000 -0.516600000 0.229005000 8 5.311307000 -0.065165000 0.078697000 8 3.999903000 -1.754096000 0.716830000 1 4.868660000 -2.151962000 0.882329000 7 1.971173000 2.371339000 -0.113775000 1 2.118423000 3.369993000 -0.168142000 1 -0.185590000 3.833683000 -0.515914000 15 Dalton Transactions Page 34 of 223 1 1.354105000 -0.707683000 1.095570000 8 -0.815036000 -1.698306000 2.077402000 1 -0.798673000 -0.737398000 2.227300000 1 -1.704979000 -1.844833000 1.715919000 8 -1.076292000 1.087485000 2.376693000 1 -0.501645000 1.556474000 1.762110000 1 -1.968849000 1.163626000 1.993471000 8 -3.572747000 -1.761900000 1.392010000 1 -3.664078000 -0.793611000 1.345153000 1 -3.893761000 -1.986057000 2.272658000 8 -3.739235000 1.048211000 1.559797000 1 -4.047063000 1.560040000 0.802358000 1 -4.312277000 1.306469000 2.292046000 6 -0.373788000 2.768522000 -0.600836000 Charge = -1 Multiplicity = 1 Sum of electronic and thermal Free Energies= -1347.558819 6 -4.427607000 -1.741387000 -1.072895000 6 -3.559594000 -1.162777000 -1.996078000 6 -2.525992000 -0.297639000 -1.559435000 6 -2.381704000 -0.047747000 -0.148852000 6 -3.298852000 -0.645225000 0.785528000 6 -4.323169000 -1.502039000 0.285854000 6 -1.628175000 0.344329000 -2.442622000 6 -1.333817000 0.807558000 0.315433000 6 -0.389597000 1.381252000 -0.607475000 6 -0.603562000 1.159556000 -1.969006000 6 0.704039000 2.205928000 -0.011482000 6 0.681886000 2.447835000 1.337168000 6 -1.262193000 1.070788000 1.703101000 6 -3.151351000 -0.357461000 2.157479000 1 -3.837555000 -0.801799000 2.870005000 1 -1.739418000 0.188614000 -3.510287000 1 -5.214157000 -2.399684000 -1.432699000 1 -3.667422000 -1.361126000 -3.056856000 1 -5.015724000 -1.954487000 0.987390000 1 0.059997000 1.618688000 -2.689084000 16 Page 35 of 223 Dalton Transactions 1 1.456658000 3.044449000 1.802959000 6 1.897685000 2.680539000 -0.679056000 8 2.741237000 3.431832000 -0.198291000 8 2.065552000 2.206472000 -1.932425000 1 2.897270000 2.571615000 -2.270202000 7 -0.249932000 1.956731000 2.155748000 1 -0.189148000 2.151731000 3.145598000 1 -2.047530000 0.729874000 3.654863000 6 -2.147756000 0.498724000 2.598088000 6 1.931286000 -1.200899000 0.274719000 8 1.515208000 -0.778521000 1.315317000 8 1.549476000 -0.893513000 -0.938781000 1 0.825690000 -0.218199000 -0.922956000 6 3.057188000 -2.248401000 0.217725000 9 3.471920000 -2.558439000 1.438811000 9 2.632140000 -3.363171000 -0.380019000 9 4.097806000 -1.784451000 -0.477091000 17 Dalton Transactions Page 36 of 223 (Transition state) Charge = -1 Multiplicity = 1 Sum of electronic and thermal Free Energies= -1347.554150 6 -4.376217000 -1.584684000 -1.107139000 6 -3.490997000 -0.968302000 -2.014720000 6 -2.454590000 -0.161942000 -1.558902000 6 -2.275807000 0.010669000 -0.141849000 6 -3.210346000 -0.575812000 0.767589000 6 -4.256631000 -1.394051000 0.245655000 6 -1.572970000 0.558300000 -2.447733000 6 -1.192020000 0.798057000 0.343872000 6 -0.155631000 1.275164000 -0.578769000 6 -0.522363000 1.280039000 -1.967098000 6 0.833888000 2.229540000 0.032544000 6 0.784942000 2.480143000 1.369911000 6 -1.137412000 1.061760000 1.714240000 6 -3.068867000 -0.319859000 2.146912000 1 -3.771298000 -0.761542000 2.845153000 1 -1.763934000 0.508441000 -3.514123000 1 -5.174747000 -2.211290000 -1.491898000 1 -3.625719000 -1.106635000 -3.082292000 1 -4.953290000 -1.853931000 0.938709000 1 0.118166000 1.800419000 -2.668764000 1 1.520524000 3.121176000 1.840346000 6 2.013200000 2.743558000 -0.637269000 8 2.797626000 3.572157000 -0.190995000 8 2.227086000 2.199401000 -1.853767000 1 3.039358000 2.589056000 -2.210894000 7 -0.129373000 1.933147000 2.193122000 1 -0.103283000 2.150304000 3.178805000 1 -1.969103000 0.734868000 3.660468000 6 -2.059709000 0.506231000 2.602752000 6 1.819141000 -1.251221000 0.307914000 8 1.652401000 -0.771818000 1.408338000 8 1.314129000 -0.898307000 -0.814974000 1 0.645330000 0.059707000 -0.711833000 6 2.759628000 -2.463094000 0.141808000 9 3.310290000 -2.822204000 1.298762000 18 Page 37 of 223 Dalton Transactions 9 2.095552000 -3.518554000 -0.343395000 9 3.748628000 -2.183803000 -0.715664000 19 Dalton Transactions Page 38 of 223 Charge = -1 Multiplicity = 1 Sum of electronic and thermal Free Energies= -1347.592203 6 -5.309173000 0.050073000 -0.902684000 6 -4.507335000 1.213690000 -0.901333000 6 -3.201004000 1.173806000 -0.466227000 6 -2.647472000 -0.066409000 -0.017421000 6 -3.484709000 -1.209222000 0.074215000 6 -4.817013000 -1.130698000 -0.407159000 6 -2.391952000 2.382832000 -0.297522000 6 -1.295613000 -0.126483000 0.401097000 6 -0.348185000 1.012839000 0.047319000 6 -1.095441000 2.329744000 0.017635000 6 0.865978000 0.964709000 0.960075000 6 1.183471000 -0.168878000 1.634205000 6 -0.858316000 -1.261992000 1.051541000 6 -2.959516000 -2.387355000 0.666321000 1 -3.587225000 -3.269653000 0.731652000 1 -2.898451000 3.338484000 -0.394099000 1 -6.328791000 0.105745000 -1.266286000 1 -4.931244000 2.159320000 -1.224067000 1 -5.440632000 -2.017739000 -0.364173000 1 -0.534897000 3.242371000 0.176261000 1 2.100700000 -0.237397000 2.206704000 6 1.890231000 2.006990000 0.972333000 8 2.801393000 2.098940000 1.775872000 8 1.765426000 2.882826000 -0.038037000 1 2.491040000 3.523081000 0.024727000 7 0.414685000 -1.280625000 1.616834000 1 0.722063000 -2.106009000 2.111894000 1 -1.297221000 -3.284519000 1.669389000 6 -1.691832000 -2.401793000 1.177162000 6 2.157161000 -0.556463000 -1.472858000 8 1.222333000 -1.367550000 -1.530283000 8 2.291475000 0.563199000 -1.989958000 1 -0.004406000 0.839073000 -0.987217000 6 3.396438000 -1.020470000 -0.657291000 9 3.124355000 -2.005888000 0.210120000 9 4.356069000 -1.482761000 -1.482378000 9 3.947014000 -0.019931000 0.047832000 20 Page 39 of 223 Dalton Transactions 2.3.2. Hydrogen Evolution Reaction Charge = 1 Multiplicity =1 Sum of electronic and thermal Free Energies= -1127.359239 6 3.194606000 0.920883000 -1.783206000 6 2.096804000 1.801067000 -1.657893000 6 0.870030000 1.346433000 -1.226881000 6 0.707598000 -0.034422000 -0.893486000 6 1.789979000 -0.929198000 -1.092642000 6 3.042859000 -0.416726000 -1.520933000 6 -0.323256000 2.195454000 -1.217062000 6 -0.547455000 -0.511644000 -0.436994000 6 -1.605611000 0.472013000 0.045127000 6 -1.486654000 1.783733000 -0.704541000 6 -2.973044000 -0.190528000 0.002641000 6 -3.082544000 -1.540817000 -0.011751000 6 -0.743158000 -1.876102000 -0.358831000 6 1.571126000 -2.316393000 -0.885413000 1 2.395522000 -3.008131000 -1.022105000 1 -0.243316000 3.170599000 -1.687767000 1 4.151979000 1.306163000 -2.114333000 1 2.211782000 2.846003000 -1.926771000 1 3.869587000 -1.107663000 -1.654586000 1 -2.357005000 2.425098000 -0.752157000 1 -4.049433000 -2.023516000 0.059534000 6 -4.215050000 0.534054000 0.264631000 8 -5.340063000 0.089020000 0.128334000 8 -4.010399000 1.772805000 0.743475000 1 -4.874241000 2.179521000 0.913824000 7 -2.013406000 -2.370010000 -0.066318000 1 -2.165119000 -3.369094000 -0.099254000 1 0.136769000 -3.846761000 -0.459018000 1 -1.373531000 0.707854000 1.100130000 8 1.205379000 1.582739000 2.022991000 1 1.046153000 0.550126000 2.111264000 1 2.227981000 1.693071000 1.724844000 1 0.625610000 1.956284000 1.342106000 21 Dalton Transactions Page 40 of 223 8 1.103781000 -0.882671000 2.298845000 1 0.465048000 -1.385525000 1.777830000 1 1.990626000 -1.142816000 1.973272000 8 3.570469000 1.656953000 1.372251000 1 3.803085000 0.703947000 1.368559000 1 4.120294000 2.068550000 2.051078000 8 3.731466000 -1.078408000 1.554265000 1 4.006183000 -1.594673000 0.785987000 1 4.286923000 -1.385059000 2.282241000 6 0.326083000 -2.784043000 -0.568057000 22 Page 41 of 223 Dalton Transactions (Transition state) Charge = 1 Multiplicity =1 Sum of electronic and thermal Free Energies= -1127.303289 6 -3.306205000 0.898714000 -1.264807000 6 -2.516572000 -0.240240000 -1.481535000 6 -1.170108000 -0.243214000 -1.149303000 6 -0.598118000 0.915252000 -0.560946000 6 -1.383359000 2.081374000 -0.387881000 6 -2.748380000 2.048100000 -0.743483000 6 -0.292860000 -1.351360000 -1.474004000 6 0.773668000 0.917254000 -0.194911000 6 1.541195000 -0.325016000 -0.228952000 6 0.993340000 -1.384127000 -1.087037000 6 2.971337000 -0.155562000 -0.040929000 6 3.466604000 1.050988000 0.371266000 6 1.338489000 2.097116000 0.276181000 6 -0.763925000 3.255614000 0.136305000 1 -1.367193000 4.146801000 0.271629000 1 -0.701521000 -2.159257000 -2.070565000 1 -4.356248000 0.881175000 -1.533110000 1 -2.951931000 -1.126617000 -1.931339000 1 -3.348305000 2.940720000 -0.601591000 1 1.630211000 -2.213872000 -1.355842000 1 4.521404000 1.190422000 0.569855000 6 3.955488000 -1.256287000 -0.078810000 8 5.151912000 -1.093831000 -0.169533000 8 3.399775000 -2.460440000 0.058969000 1 4.099633000 -3.133680000 0.042786000 7 2.679266000 2.117434000 0.570039000 1 3.096570000 2.985032000 0.892815000 1 1.042778000 4.168603000 0.823844000 1 1.168503000 -0.961399000 1.159693000 8 -0.831163000 -1.737605000 1.789056000 1 -1.446716000 -0.964472000 1.903826000 1 -1.245557000 -2.290163000 1.079220000 1 0.339345000 -1.297377000 1.450650000 8 -2.684866000 0.137087000 2.031812000 23 Dalton Transactions Page 42 of 223 1 -2.512178000 0.999643000 1.638169000 1 -3.396711000 -0.261307000 1.496705000 8 -2.334637000 -3.088181000 0.019694000 1 -3.159367000 -2.598532000 0.200792000 1 -2.501491000 -3.986231000 0.327953000 8 -4.504713000 -1.460522000 0.670265000 1 -5.050372000 -1.140789000 -0.058247000 1 -5.122157000 -1.870122000 1.288915000 6 0.562069000 3.274280000 0.444090000 24 Page 43 of 223 Dalton Transactions Charge = 1 Multiplicity =1 Sum of electronic and thermal Free Energies= -1127.369125 6 -2.934456000 1.372643000 -1.410944000 6 -2.249943000 0.201095000 -1.712355000 6 -0.918628000 0.033173000 -1.311457000 6 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-3.531907000 -0.006096000 1 0.247713000 -2.576506000 -0.143059000 1 -0.027349000 -3.604693000 0.933010000 70 Page 89 of 223 Dalton Transactions Charge = 0 Multiplicity = 1 Sum of electronic and thermal Free Energies= -648.883699 6 -2.893022000 -0.005087000 -0.296965000 6 -3.469674000 1.268970000 -0.178275000 6 -3.692776000 -1.127964000 -0.034598000 6 -4.802264000 1.408499000 0.188899000 6 -5.024190000 -0.975860000 0.331395000 6 -5.593416000 0.290839000 0.446574000 1 -2.860573000 2.144662000 -0.379098000 1 -3.256936000 -2.118038000 -0.123401000 1 -5.225173000 2.403540000 0.276980000 1 -5.621358000 -1.858940000 0.532026000 1 -6.631633000 0.404598000 0.733685000 7 -1.580432000 -0.153209000 -0.719945000 6 2.796229000 -0.111780000 -0.017698000 6 3.749735000 -1.124134000 0.118042000 6 3.154554000 1.232895000 -0.040547000 6 5.082713000 -0.769305000 0.231982000 6 4.495127000 1.579910000 0.076109000 6 5.452750000 0.579163000 0.211220000 1 3.433842000 -2.160053000 0.130811000 1 2.377605000 1.981548000 -0.148516000 1 5.840834000 -1.535992000 0.337976000 1 4.792147000 2.621384000 0.062018000 1 6.499387000 0.846394000 0.301733000 7 1.392032000 -0.364958000 -0.142782000 1 -1.131535000 -1.020163000 -0.452488000 8 1.068105000 -1.524705000 -0.113362000 1 -0.977235000 0.638995000 -0.542575000 71 Dalton Transactions Page 90 of 223 Charge = 0 Multiplicity = 1 Sum of electronic and thermal Free Energies= -648.926788 8 0.156242000 3.013141000 0.505492000 6 1.756557000 -0.518634000 -0.058728000 6 2.607716000 -1.478876000 0.485934000 6 2.274010000 0.640463000 -0.643748000 6 3.980115000 -1.261468000 0.489721000 6 3.647018000 0.840908000 -0.651595000 6 4.499899000 -0.101728000 -0.077706000 1 2.177890000 -2.378883000 0.910716000 1 1.608740000 1.356257000 -1.110822000 1 4.643287000 -1.999415000 0.925539000 1 4.056291000 1.732622000 -1.111888000 1 5.570994000 0.063987000 -0.086483000 7 0.367913000 -0.820365000 -0.010439000 6 -1.779001000 -0.117771000 -0.051434000 6 -2.616015000 0.994648000 0.015574000 6 -2.312681000 -1.407570000 -0.123763000 6 -3.995417000 0.820909000 0.019966000 6 -3.689258000 -1.570922000 -0.120798000 6 -4.532154000 -0.460252000 -0.047870000 1 -2.173195000 1.983280000 0.065456000 1 -1.648702000 -2.260309000 -0.184484000 1 -4.647461000 1.684720000 0.072319000 1 -4.111355000 -2.567476000 -0.180080000 1 -5.607191000 -0.598747000 -0.048367000 7 -0.382297000 0.166511000 -0.056232000 1 -0.121463000 3.116040000 1.421552000 1 0.058183000 2.061537000 0.335982000 72 Page 91 of 223 Dalton Transactions 2.3.5. Thermodynamic assessment of protonation steps Reactants in order to make this evaluation: addition of the Free energies of the products of hydride transfer processes to the free energy of Trifluoroacetica acid molecule . Charge = 0 Multiplicity = 1 Sum of electronic and thermal Free Energies= -526.775920 8 -1.473787000 1.221330000 -0.001979000 6 -0.941748000 0.151928000 -0.004002000 8 -1.509495000 -1.033177000 -0.002052000 6 0.589057000 -0.002565000 -0.001437000 9 0.992615000 -0.630301000 1.104548000 9 0.996086000 -0.718092000 -1.050180000 9 1.173546000 1.186117000 -0.047782000 1 -2.477824000 -0.940924000 0.005597000 Product in order to make this evaluation: addition of the Free energies of the products of protonation (inckuding carboxylate) to the free energy of model organic fragment shown below generated as a result of hydide transfer. Charge = 1 Multiplicity = 1 Sum of electronic and thermal Free Energies= -820.546340 6 -4.074661000 -1.199152000 -0.009765000 6 -2.976234000 -2.049425000 -0.040520000 6 -1.675928000 -1.530983000 -0.038412000 6 -1.489313000 -0.130361000 -0.004697000 6 -2.611754000 0.733748000 0.021759000 6 -3.896966000 0.179058000 0.020343000 6 -0.519158000 -2.369107000 -0.080233000 6 -0.172333000 0.401524000 -0.001955000 6 0.969835000 -0.452304000 -0.020956000 6 0.744753000 -1.864818000 -0.075446000 6 2.248310000 0.173130000 -0.012191000 6 2.327672000 1.547826000 -0.008865000 6 -0.025434000 1.804027000 0.018846000 6 -2.398990000 2.149211000 0.047157000 73 Dalton Transactions Page 92 of 223 1 -3.264058000 2.802979000 0.066156000 1 -0.667628000 -3.443015000 -0.122023000 1 -5.076146000 -1.611450000 -0.011009000 1 -3.115241000 -3.124647000 -0.067437000 1 -4.755713000 0.841274000 0.042051000 1 1.586190000 -2.537153000 -0.116425000 1 3.275772000 2.067713000 -0.013300000 6 3.583386000 -0.501283000 -0.006624000 8 4.601437000 0.082339000 -0.289529000 8 3.555577000 -1.772610000 0.366428000 1 4.459841000 -2.127741000 0.342349000 7 1.230236000 2.311624000 0.009527000 1 1.344698000 3.324274000 0.022579000 1 -0.974496000 3.745801000 0.059763000 6 -1.146681000 2.676036000 0.044129000 74 Page 93 of 223 Dalton Transactions Charge = -1 Multiplicity = 1 Sum of electronic and thermal Free Energies= -964.165898 1 -1.193708000 -2.550054000 0.553844000 8 -1.586369000 -2.265276000 1.388768000 8 -3.320831000 -1.240662000 -0.869041000 6 -1.820363000 0.398224000 -0.648754000 6 -0.748088000 1.034607000 -1.266873000 6 -2.284734000 0.798155000 0.605803000 6 -0.118615000 2.089981000 -0.618377000 6 -1.653489000 1.852700000 1.244246000 6 -0.573392000 2.494718000 0.633472000 1 -0.416428000 0.679394000 -2.236011000 1 -3.113879000 0.272754000 1.062325000 1 0.723410000 2.589922000 -1.081478000 1 -1.992381000 2.175447000 2.221374000 1 -0.078664000 3.312578000 1.145060000 7 -2.383335000 -0.689919000 -1.389492000 8 0.670432000 -1.775472000 -0.413958000 1 -0.932100000 -1.602739000 1.668791000 6 1.072474000 -0.902073000 0.368782000 8 0.637364000 -0.540957000 1.474582000 6 2.358484000 -0.177257000 -0.114758000 9 3.418587000 -1.000497000 -0.018601000 9 2.274422000 0.191097000 -1.403142000 9 2.650176000 0.920149000 0.591575000 75 Dalton Transactions Page 94 of 223 Charge = -1 Multiplicity = 1 Sum of electronic and thermal Free Energies= -888.967034 1 0.149739000 -1.705490000 -0.722451000 8 -0.773209000 -1.887240000 -1.022094000 6 -2.427971000 -0.635158000 0.077879000 6 -2.130729000 0.498482000 -0.681886000 6 -3.593600000 -0.660969000 0.853247000 6 -2.994151000 1.589293000 -0.660014000 6 -4.442056000 0.437518000 0.870582000 6 -4.151184000 1.571133000 0.112936000 1 -1.228069000 0.516840000 -1.278142000 1 -3.826164000 -1.545824000 1.437815000 1 -2.753544000 2.463726000 -1.255044000 1 -5.342502000 0.403819000 1.474290000 1 -4.817767000 2.425263000 0.125311000 7 -1.541476000 -1.724237000 0.144817000 8 1.633765000 -1.317783000 -0.054155000 1 -2.038530000 -2.595267000 0.307014000 6 1.960818000 -0.154929000 -0.363469000 8 1.395183000 0.672593000 -1.082867000 6 3.276755000 0.352287000 0.280327000 9 4.025022000 -0.626713000 0.798000000 9 4.038485000 1.010851000 -0.604699000 9 3.004711000 1.213649000 1.277011000 76 Page 95 of 223 Dalton Transactions Charge = -1 Multiplicity = 1 Sum of electronic and thermal Free Energies= -890.218175 6 -1.381901000 0.362572000 0.795121000 6 -2.007794000 1.220018000 -0.123288000 6 -1.825922000 -0.966200000 0.876976000 6 -3.043021000 0.760982000 -0.927112000 6 -2.859753000 -1.414994000 0.064694000 6 -3.481827000 -0.558905000 -0.841454000 1 -1.660316000 2.244660000 -0.204267000 1 -1.335649000 -1.643933000 1.568565000 1 -3.507497000 1.442532000 -1.632154000 1 -3.179318000 -2.448975000 0.140071000 1 -4.287233000 -0.914407000 -1.472924000 7 -0.380893000 0.836316000 1.632600000 1 0.256213000 0.120608000 1.962553000 1 0.103744000 1.654171000 1.274526000 8 1.422880000 -1.644339000 1.392547000 8 0.823632000 3.221946000 0.149989000 1 0.110473000 3.864768000 0.070836000 1 0.786460000 2.724111000 -0.674324000 6 1.335668000 -1.494670000 0.163575000 8 0.830516000 -2.216034000 -0.705923000 6 1.968182000 -0.194405000 -0.412521000 9 2.482819000 0.615750000 0.519328000 9 2.958765000 -0.485266000 -1.273002000 9 1.063011000 0.527658000 -1.105207000 77 Dalton Transactions Page 96 of 223 Charge = -1 Multiplicity = 1 Sum of electronic and thermal Free Energies= -1175.262559 8 0.887934000 -1.650436000 -2.109452000 6 -0.280883000 1.448783000 -0.453526000 6 -1.205521000 0.992621000 -1.390645000 6 -0.635923000 2.423496000 0.481399000 6 -2.507028000 1.479653000 -1.370691000 6 -1.930908000 2.919746000 0.480825000 6 -2.869116000 2.445026000 -0.437256000 1 -0.901663000 0.231536000 -2.100768000 1 0.099173000 2.780140000 1.191847000 1 -3.232926000 1.102087000 -2.081381000 1 -2.215442000 3.679395000 1.199885000 1 -3.882174000 2.830411000 -0.421646000 7 1.011920000 0.859505000 -0.537865000 6 3.041640000 0.456595000 0.328013000 6 3.715120000 0.227890000 1.526372000 6 3.642967000 0.144291000 -0.894291000 6 4.977855000 -0.352025000 1.509664000 6 4.910228000 -0.419775000 -0.903392000 6 5.575214000 -0.676987000 0.295562000 1 3.230078000 0.497285000 2.457629000 1 3.131474000 0.370791000 -1.821724000 1 5.496787000 -0.543540000 2.441501000 1 5.386731000 -0.654580000 -1.848141000 1 6.564882000 -1.118761000 0.279513000 7 1.748591000 1.039559000 0.444111000 8 -0.783239000 -1.910317000 0.119071000 1 0.301789000 -1.937591000 -1.385773000 1 1.138582000 -0.763243000 -1.813719000 6 -1.952171000 -1.708026000 -0.264166000 8 -2.484817000 -1.917579000 -1.357554000 6 -2.864147000 -1.120417000 0.845780000 9 -2.289428000 -0.085189000 1.473295000 9 -4.048085000 -0.698232000 0.387158000 9 -3.118472000 -2.050573000 1.786287000 78 Page 97 of 223 Dalton Transactions Charge = -1 Multiplicity = 1 Sum of electronic and thermal Free Energies= -1100.044317 6 2.355092000 -0.084085000 -0.036143000 6 3.074543000 0.957873000 -0.639372000 6 3.051245000 -1.084042000 0.651461000 6 4.459718000 0.988903000 -0.559383000 6 4.439712000 -1.038215000 0.724011000 6 5.156506000 -0.008404000 0.121416000 1 2.534426000 1.740890000 -1.162092000 1 2.500294000 -1.887578000 1.124164000 1 4.998184000 1.803689000 -1.031402000 1 4.965137000 -1.822358000 1.258844000 1 6.237925000 0.019151000 0.181973000 7 0.968236000 -0.121186000 -0.202146000 6 -0.698887000 -1.758709000 0.268289000 6 -1.781738000 -2.117201000 1.081585000 6 -0.545291000 -2.376577000 -0.977079000 6 -2.683280000 -3.084518000 0.657844000 6 -1.458448000 -3.340265000 -1.389829000 6 -2.530720000 -3.705747000 -0.580390000 1 -1.909735000 -1.627177000 2.041684000 1 0.286058000 -2.094274000 -1.610769000 1 -3.517805000 -3.348171000 1.298645000 1 -1.326788000 -3.811049000 -2.358377000 1 -3.238480000 -4.456825000 -0.910382000 7 0.236680000 -0.836874000 0.746337000 1 -0.107426000 -0.259628000 1.507229000 8 0.031413000 2.673613000 -0.334767000 1 0.558719000 0.789843000 -0.416440000 6 -1.158191000 3.012207000 -0.184892000 8 -1.684302000 4.127218000 -0.204327000 6 -2.106131000 1.813010000 0.092242000 9 -3.400985000 2.128539000 0.021904000 9 -1.892419000 0.805173000 -0.770571000 9 -1.888439000 1.311607000 1.326644000 79 Dalton Transactions Page 98 of 223 Charge = -1 Multiplicity = 1 Sum of electronic and thermal Free Energies= -1101.264872 6 2.816497000 -0.760774000 0.760843000 6 4.099408000 -1.262461000 1.029210000 6 2.349941000 -0.796783000 -0.563975000 6 4.886147000 -1.778552000 0.006236000 6 3.146779000 -1.311744000 -1.577741000 6 4.421085000 -1.808132000 -1.306443000 1 4.471340000 -1.239670000 2.048771000 1 1.353720000 -0.426677000 -0.778142000 1 5.875376000 -2.157584000 0.240003000 1 2.765355000 -1.325565000 -2.593150000 1 5.038529000 -2.208064000 -2.101579000 7 2.002727000 -0.295072000 1.781240000 6 -2.285468000 -1.398046000 0.283754000 6 -3.075038000 -0.272865000 -0.008790000 6 -2.867091000 -2.670039000 0.164459000 6 -4.397495000 -0.425418000 -0.405149000 6 -4.190799000 -2.808589000 -0.234486000 6 -4.970099000 -1.690643000 -0.524033000 1 -2.646219000 0.720386000 0.079510000 1 -2.267704000 -3.546286000 0.390801000 1 -4.987128000 0.458535000 -0.624136000 1 -4.616843000 -3.802798000 -0.317627000 1 -6.001881000 -1.802212000 -0.834447000 7 -0.950500000 -1.251261000 0.625554000 1 -0.707340000 -0.357447000 1.044863000 1 2.492747000 -0.052074000 2.631949000 1 1.305902000 0.403546000 1.526706000 8 -0.331544000 1.482880000 1.596023000 6 0.143571000 2.412929000 -0.505905000 9 0.011879000 3.559166000 -1.183492000 9 1.455159000 2.254026000 -0.255433000 9 -0.205306000 1.419917000 -1.356433000 1 -0.540211000 -2.037019000 1.112554000 6 -0.730539000 2.340019000 0.778925000 8 -1.710733000 3.077855000 0.791871000 80 Page 99 of 223 Dalton Transactions + Charge = 1 Multiplicity = 1 Sum of electronic and thermal Free Energies= -820.546340 6 -4.074661000 -1.199152000 -0.009765000 6 -2.976234000 -2.049425000 -0.040520000 6 -1.675928000 -1.530983000 -0.038412000 6 -1.489313000 -0.130361000 -0.004697000 6 -2.611754000 0.733748000 0.021759000 6 -3.896966000 0.179058000 0.020343000 6 -0.519158000 -2.369107000 -0.080233000 6 -0.172333000 0.401524000 -0.001955000 6 0.969835000 -0.452304000 -0.020956000 6 0.744753000 -1.864818000 -0.075446000 6 2.248310000 0.173130000 -0.012191000 6 2.327672000 1.547826000 -0.008865000 6 -0.025434000 1.804027000 0.018846000 6 -2.398990000 2.149211000 0.047157000 1 -3.264058000 2.802979000 0.066156000 1 -0.667628000 -3.443015000 -0.122023000 1 -5.076146000 -1.611450000 -0.011009000 1 -3.115241000 -3.124647000 -0.067437000 1 -4.755713000 0.841274000 0.042051000 1 1.586190000 -2.537153000 -0.116425000 1 3.275772000 2.067713000 -0.013300000 6 3.583386000 -0.501283000 -0.006624000 8 4.601437000 0.082339000 -0.289529000 8 3.555577000 -1.772610000 0.366428000 1 4.459841000 -2.127741000 0.342349000 7 1.230236000 2.311624000 0.009527000 1 1.344698000 3.324274000 0.022579000 1 -0.974496000 3.745801000 0.059763000 6 -1.146681000 2.676036000 0.044129000 81 Dalton Transactions Page 100 of 223 2.4.PBE-D2 Optimized geometries associated with the Organic Catalyst: ox-CF 2.4.1. Hydrogen Evolution Reaction Charge = 1 Multiplicity =1 Sum of electronic and thermal Free Energies= -1126.527429 6 -3.383431 0.655284 -1.625123 6 -2.484535 -0.424027 -1.820431 6 -1.181563 -0.364185 -1.335097 6 -0.739142 0.798789 -0.615229 6 -1.629997 1.918812 -0.479423 6 -2.959988 1.809758 -0.977139 6 -0.199076 -1.405577 -1.618634 6 0.579173 0.857920 -0.089107 6 1.454636 -0.399441 -0.012522 6 1.038956 -1.407633 -1.068942 6 2.935110 -0.002833 -0.006757 6 3.285387 1.245353 0.429053 6 1.033659 2.076681 0.424062 6 -1.146105 3.105363 0.137783 1 -1.822645 3.955543 0.253660 1 -0.484347 -2.187522 -2.328976 1 -4.403307 0.586098 -2.010345 1 -2.805863 -1.309412 -2.374821 1 -3.636509 2.659548 -0.853544 1 1.751471 -2.190801 -1.325788 1 4.333685 1.522626 0.545603 6 4.056278 -0.932498 -0.196895 8 5.239523 -0.617420 -0.296937 8 3.671308 -2.247487 -0.200498 1 4.494949 -2.767632 -0.319977 7 2.376418 2.201962 0.770290 1 2.713691 3.113556 1.076180 1 0.562216 4.119393 0.980860 1 1.253681 -0.888782 0.971423 8 -0.892664 -2.635429 1.105210 1 -0.925372 -1.703485 1.629835 1 -1.930072 -2.847227 0.864736 82 Page 101 of 223 Dalton Transactions 1 -0.415541 -2.475771 0.248305 8 -1.212237 -0.464900 2.308808 1 -0.657538 0.285093 2.016138 1 -2.142478 -0.236946 2.031498 8 -3.300336 -2.920758 0.585957 1 -3.663619 -2.026021 0.836092 1 -3.769648 -3.575537 1.138439 8 -3.727964 -0.355378 1.323988 1 -3.789509 0.218973 0.526269 1 -4.471447 -0.093858 1.902033 6 0.166011 3.194802 0.552422 83 Dalton Transactions Page 102 of 223 (Transition state) Charge = 1 Multiplicity =1 Sum of electronic and thermal Free Energies= -1126.496841 6 -3.374540 -0.235356 -1.930788 6 -2.337542 -1.187500 -1.996591 6 -1.059775 -0.892950 -1.506643 6 -0.816024 0.385988 -0.911693 6 -1.865116 1.361049 -0.866552 6 -3.143991 1.024423 -1.380758 6 0.048650 -1.808457 -1.644779 6 0.478160 0.700800 -0.413929 6 1.518994 -0.338731 -0.322123 6 1.277686 -1.542975 -1.130090 6 2.872699 0.175224 -0.087296 6 3.037018 1.484938 0.314611 6 0.716783 2.002314 0.061091 6 -1.586226 2.648777 -0.316049 1 -2.390656 3.386528 -0.267275 1 -0.121296 -2.732524 -2.203622 1 -4.361711 -0.483444 -2.327472 1 -2.517298 -2.164949 -2.451076 1 -3.939292 1.773586 -1.346023 1 2.094615 -2.250546 -1.254184 1 4.022474 1.884147 0.553071 6 4.119440 -0.626681 -0.081955 8 5.245997 -0.150216 -0.118308 8 3.897274 -1.963464 0.026249 1 4.781049 -2.393217 0.034543 7 1.997683 2.336637 0.449973 1 2.176867 3.289792 0.772024 1 -0.092183 3.963181 0.524255 1 1.202432 -0.965343 1.043198 8 -0.373134 -1.346427 2.619239 1 -0.872608 -0.460818 2.630926 1 -1.007907 -1.969890 2.122309 1 0.593058 -1.150322 1.732596 8 -1.861377 0.831919 2.513570 84 Page 103 of 223 Dalton Transactions 1 -1.542477 1.525775 1.907120 1 -2.662844 0.454294 2.072208 8 -2.119981 -2.763300 1.249096 1 -2.845313 -2.091867 1.187046 1 -2.505047 -3.497850 1.761539 8 -3.862148 -0.629593 1.298922 1 -4.082017 -0.307631 0.400998 1 -4.716250 -0.728664 1.761819 6 -0.321286 2.971130 0.127887 85 Dalton Transactions Page 104 of 223 Charge = 1 Multiplicity =1 Sum of electronic and thermal Free Energies= -1126.537031 6 -2.960735 1.388398 -1.326475 6 -2.322706 0.161237 -1.536740 6 -0.974193 -0.018720 -1.162591 6 -0.264192 1.067477 -0.570416 6 -0.923248 2.318512 -0.351285 6 -2.274352 2.454714 -0.735199 6 -0.292167 -1.259464 -1.349278 6 1.094894 0.893829 -0.188557 6 1.768473 -0.363310 -0.386194 6 1.023947 -1.427948 -0.983924 6 3.141525 -0.442452 0.025226 6 3.746643 0.680055 0.578669 6 1.764481 1.997873 0.407125 6 -0.199455 3.390639 0.260071 1 -0.713655 4.339786 0.427863 1 -0.856560 -2.093840 -1.770286 1 -4.004582 1.518368 -1.621775 1 -2.855820 -0.681002 -1.981906 1 -2.777929 3.408618 -0.560836 1 1.505762 -2.389028 -1.143120 1 4.788586 0.673795 0.895051 6 4.063611 -1.619883 -0.077619 8 5.276741 -1.524013 0.020778 8 3.434673 -2.801486 -0.258708 1 4.134301 -3.490219 -0.313725 7 3.073734 1.830145 0.761546 1 3.565683 2.621418 1.188863 1 1.677688 4.052043 1.098622 1 -0.106430 -0.667223 1.790832 8 -2.499388 -2.512529 2.335547 1 -2.789292 -1.571413 2.379683 1 -2.575308 -2.697743 1.370985 1 -0.663814 -1.158200 1.934791 8 -3.239824 0.202266 1.990962 1 -2.446002 0.427965 1.471937 1 -3.899690 -0.039875 1.300462 86 Page 105 of 223 Dalton Transactions 8 -3.014322 -2.773784 -0.457083 1 -3.767547 -2.143816 -0.352172 1 -3.442969 -3.631618 -0.626769 8 -4.986371 -0.895091 0.101498 1 -5.331050 -0.345543 -0.628188 1 -5.775728 -1.274450 0.533537 6 1.115165 3.240386 0.632417 87 Dalton Transactions Page 106 of 223 Charge = 0 Multiplicity = 1 Sum of electronic and thermal Free Energies= -1347.061464 6 -2.271086 3.048663 0.651999 6 -1.056668 3.312902 -0.027929 6 -0.010994 2.391043 -0.016498 6 -0.179085 1.145093 0.683638 6 -1.383160 0.916080 1.434951 6 -2.426704 1.881913 1.381832 6 1.302483 2.684096 -0.579916 6 0.849453 0.170255 0.654756 6 1.987157 0.288527 -0.361333 6 2.268201 1.746083 -0.678265 6 3.185760 -0.553010 0.086079 6 2.999246 -1.570418 0.984035 6 0.732642 -0.944764 1.485793 6 -1.493541 -0.284143 2.191056 1 -2.415366 -0.479068 2.744652 1 1.497552 3.714775 -0.892879 1 -3.078877 3.783698 0.614543 1 -0.918615 4.264376 -0.549612 1 -3.350823 1.683181 1.931140 1 3.250400 2.000953 -1.075936 1 3.819251 -2.240654 1.245057 6 4.503645 -0.526025 -0.554483 8 5.506180 -1.132190 -0.177514 8 4.528287 0.227289 -1.700792 1 5.445774 0.160403 -2.041631 7 1.803134 -1.837017 1.574557 1 1.738348 -2.607805 2.236957 1 -0.504912 -2.086035 2.852479 1 1.592277 -0.150641 -1.307104 6 -0.444597 -1.180108 2.243002 6 -3.120441 -1.483106 -0.839687 9 -2.666706 -2.555551 -0.160353 9 -3.941962 -0.780374 -0.025320 9 -3.859361 -1.929851 -1.890323 6 -1.928311 -0.640090 -1.368493 88 Page 107 of 223 Dalton Transactions 8 -0.826134 -1.113599 -1.524215 8 -2.335414 0.600238 -1.648063 1 -1.552027 1.136058 -1.914136 89 Dalton Transactions Page 108 of 223 (Transition state) Charge = 0 Multiplicity = 1 Sum of electronic and thermal Free Energies= -1347.030890 6 -2.258325 3.640170 -0.082933 6 -0.976887 3.714611 -0.660489 6 -0.023634 2.714169 -0.425052 6 -0.366031 1.610794 0.419400 6 -1.653152 1.563448 1.044623 6 -2.592443 2.585558 0.762016 6 1.322702 2.786311 -0.944928 6 0.583527 0.580571 0.657058 6 1.818340 0.513606 -0.140197 6 2.213055 1.770013 -0.790018 6 2.806872 -0.452937 0.344590 6 2.443970 -1.367187 1.313669 6 0.264674 -0.425830 1.585243 6 -1.948859 0.483184 1.930151 1 -2.939351 0.435904 2.388725 1 1.620946 3.698367 -1.469391 1 -2.989610 4.424788 -0.289915 1 -0.709071 4.561903 -1.297564 1 -3.581045 2.533993 1.225415 1 3.219334 1.847452 -1.196708 1 3.141698 -2.129671 1.658650 6 4.159107 -0.659849 -0.220925 8 5.052221 -1.294259 0.326220 8 4.310544 -0.112240 -1.457518 1 5.230697 -0.310865 -1.738011 7 1.218607 -1.377711 1.876066 1 0.988988 -2.108361 2.551593 1 -1.220754 -1.299423 2.903974 1 1.290859 -0.201608 -1.449137 6 -1.007222 -0.478521 2.215884 6 -2.639974 -1.896066 -0.758387 9 -2.893132 -2.539241 0.410383 9 -3.292076 -0.703671 -0.712015 90 Page 109 of 223 Dalton Transactions 9 -3.217344 -2.631112 -1.755729 6 -1.104243 -1.756767 -1.020018 8 -0.348554 -2.579444 -0.509622 8 -0.844404 -0.763040 -1.804829 1 0.432698 -0.502082 -1.715975 91 Dalton Transactions Page 110 of 223 Charge = 0 Multiplicity = 1 Sum of electronic and thermal Free Energies= -1347.090569 6 3.969944 -3.657528 0.177401 6 4.571342 -2.398773 0.279382 6 3.799296 -1.223908 0.166070 6 2.393274 -1.331768 -0.057089 6 1.783957 -2.622042 -0.164401 6 2.592928 -3.771426 -0.042235 6 4.372605 0.082664 0.258968 6 1.604281 -0.153037 -0.172365 6 2.195866 1.153195 -0.056311 6 3.612160 1.223291 0.153367 6 1.319775 2.278572 -0.186811 6 -0.034927 2.050541 -0.435051 6 0.207560 -0.295776 -0.410489 6 0.373176 -2.708576 -0.396600 1 -0.081220 -3.698993 -0.478517 1 5.451144 0.163909 0.418051 1 4.579511 -4.558946 0.269348 1 5.647278 -2.309535 0.449674 1 2.124544 -4.755622 -0.122488 1 4.090730 2.196223 0.230151 1 -0.730971 2.882958 -0.544005 6 1.676552 3.728136 -0.093509 8 0.943213 4.624668 -0.482652 8 2.872309 3.969341 0.492884 1 2.995018 4.944757 0.493869 7 -0.557867 0.823507 -0.537192 1 -1.672942 0.694778 -0.664482 1 -1.474509 -1.637878 -0.709566 1 -0.414671 1.277456 2.632998 6 -0.400567 -1.580513 -0.520071 6 -5.033438 -0.491974 0.109472 92 Page 111 of 223 Dalton Transactions 9 -5.832586 0.245680 -0.715122 9 -4.918007 -1.733649 -0.457337 9 -5.707062 -0.652433 1.277252 6 -3.624358 0.157729 0.299352 8 -3.063595 0.397794 -0.826694 8 -3.215361 0.333284 1.452403 1 -1.059035 1.066423 2.300160 93 Dalton Transactions Page 112 of 223 2.4.2. Hydride transfer processes Charge = 0 Multiplicity = 1 Sum of electronic and thermal Free Energies= -1256.946231 6 -2.945481 3.210722 0.459362 6 -1.685358 3.560679 -0.084360 6 -0.596760 2.695928 0.007878 6 -0.762595 1.422931 0.655720 6 -2.019798 1.107033 1.277116 6 -3.107098 2.015269 1.141083 6 0.748951 3.084374 -0.397754 6 0.327132 0.518097 0.736186 6 1.574060 0.739698 -0.121879 6 1.784424 2.217930 -0.387263 6 2.764470 -0.026736 0.456616 6 2.545010 -1.072988 1.312653 6 0.198656 -0.606453 1.554863 6 -2.124447 -0.098280 2.025418 1 -3.080860 -0.352028 2.489982 1 0.907381 4.130641 -0.678029 1 -3.784345 3.904711 0.363643 1 -1.548962 4.535389 -0.561747 1 -4.066002 1.755717 1.598490 1 2.784825 2.545731 -0.669478 1 3.371939 -1.694926 1.657769 6 4.144080 0.103928 -0.021316 8 5.136723 -0.423599 0.479225 8 4.247857 0.860833 -1.160508 1 5.202266 0.866716 -1.388262 7 1.309190 -1.427034 1.756622 1 1.217693 -2.218745 2.390418 1 -1.087449 -1.826023 2.801349 1 1.342823 0.300447 -1.122280 6 -1.028198 -0.920189 2.192178 8 -0.239971 0.034156 -2.672777 8 -2.324484 0.397857 -2.121721 6 -1.315723 -1.558656 -1.352616 6 -0.134723 -2.303579 -1.250136 94 Page 113 of 223 Dalton Transactions 6 -2.517200 -1.978017 -0.771016 6 -0.162596 -3.500299 -0.531337 6 -2.531150 -3.185787 -0.068190 6 -1.358188 -3.943470 0.055279 1 0.781203 -1.936376 -1.713538 1 -3.411469 -1.363895 -0.873520 1 0.752233 -4.087171 -0.427429 1 -3.459814 -3.531521 0.390523 1 -1.373962 -4.883293 0.612036 7 -1.293950 -0.286130 -2.098705 95 Dalton Transactions Page 114 of 223 (Transition state) Charge = 0 Multiplicity = 1 Sum of electronic and thermal Free Energies= -1256.935085 6 2.589867 3.639215 -0.191058 6 1.278887 3.822023 0.291767 6 0.290301 2.847729 0.086278 6 0.640166 1.639816 -0.602245 6 1.972639 1.464889 -1.105526 6 2.933498 2.487239 -0.888744 6 -1.078539 3.032411 0.503871 6 -0.330651 0.614087 -0.772465 6 -1.646277 0.705376 -0.091359 6 -2.008394 2.040197 0.381633 6 -2.646423 -0.301422 -0.547737 6 -2.213414 -1.379307 -1.282688 6 0.030521 -0.533441 -1.499796 6 2.289178 0.266257 -1.810566 1 3.304515 0.133409 -2.192209 1 -1.360248 3.998378 0.931578 1 3.338809 4.416882 -0.021666 1 1.012503 4.741113 0.820977 1 3.947368 2.345777 -1.272441 1 -3.030373 2.207607 0.717347 1 -2.896741 -2.178315 -1.568328 6 -4.066095 -0.371262 -0.149921 8 -4.898018 -1.133294 -0.634893 8 -4.390991 0.482431 0.864047 1 -5.346428 0.342351 1.041127 7 -0.919757 -1.531957 -1.669870 1 -0.656555 -2.365773 -2.194389 1 1.562693 -1.617806 -2.578456 1 -1.209345 0.170341 1.113943 6 1.330871 -0.702154 -2.028926 8 -0.682435 -0.420541 2.029599 8 1.306801 0.593379 2.222844 6 1.226334 -1.543699 1.258581 96 Page 115 of 223 Dalton Transactions 6 0.443391 -2.655611 0.883717 6 2.621391 -1.536842 1.052281 6 1.066903 -3.747407 0.279253 6 3.223916 -2.644367 0.452971 6 2.454538 -3.748881 0.056204 1 -0.631087 -2.644612 1.063534 1 3.197951 -0.664923 1.360192 1 0.463029 -4.607840 -0.019546 1 4.303935 -2.640919 0.286232 1 2.932526 -4.609550 -0.417191 7 0.629604 -0.406756 1.873210 97 Dalton Transactions Page 116 of 223 Charge = 0 Multiplicity = 1 Sum of electronic and thermal Free Energies= -1256.944633 6 -2.891221 -1.676066 1.502614 6 -2.209577 -0.484100 1.789413 6 -0.866897 -0.307239 1.392984 6 -0.202667 -1.368915 0.698574 6 -0.902568 -2.590559 0.419868 6 -2.255671 -2.717406 0.827673 6 -0.150047 0.904228 1.633689 6 1.153052 -1.203530 0.282878 6 1.864042 0.034390 0.544326 6 1.203670 1.028453 1.289165 6 3.216353 0.128451 0.012434 6 3.784988 -0.979065 -0.592169 6 1.784398 -2.283637 -0.378436 6 -0.216439 -3.637027 -0.264695 1 -0.753478 -4.564067 -0.480348 1 -0.633987 1.691167 2.214043 1 -3.933496 -1.788108 1.811571 1 -2.710102 0.323231 2.328326 1 -2.787420 -3.646269 0.605533 1 1.735610 1.938192 1.564264 1 4.801739 -0.953222 -0.982923 6 4.064882 1.341993 -0.035942 8 5.264071 1.349016 -0.285962 8 3.369275 2.497570 0.170726 1 4.014598 3.231500 0.073949 7 3.107205 -2.132261 -0.762733 1 3.569012 -2.913478 -1.231520 1 1.633780 -4.292768 -1.170693 1 0.851711 2.239735 -0.399047 6 1.101153 -3.492187 -0.651258 8 0.116900 2.399862 -1.038390 8 -1.226478 3.527631 0.477459 6 -2.095430 1.656050 -0.652625 6 -1.851644 0.547190 -1.494688 6 -3.402470 1.907831 -0.182421 6 -2.914213 -0.265586 -1.884513 98 Page 117 of 223 Dalton Transactions 6 -4.455988 1.083389 -0.590490 6 -4.224347 -0.005928 -1.441911 1 -0.834850 0.346797 -1.828966 1 -3.564558 2.760060 0.478656 1 -2.717907 -1.118807 -2.539056 1 -5.467435 1.295735 -0.234128 1 -5.049992 -0.649412 -1.754101 7 -1.041995 2.444077 -0.150560 99 Dalton Transactions Page 118 of 223 Charge = 0 Multiplicity = 1 Sum of electronic and thermal Free Energies= -1467.828706 6 -0.021320 -3.395865 2.492009 6 -1.144968 -2.557438 2.289795 6 -0.990048 -1.232930 1.886297 6 0.333015 -0.715976 1.662749 6 1.472044 -1.542296 1.956159 6 1.262958 -2.895723 2.345121 6 -2.111226 -0.304699 1.799953 6 0.508158 0.621540 1.223118 6 -0.681934 1.400996 0.662295 6 -1.975021 0.946063 1.309868 6 -0.396617 2.903446 0.681718 6 0.896029 3.347052 0.777960 6 1.794512 1.161065 1.229036 6 2.770382 -0.968523 1.860538 1 3.643020 -1.593317 2.068051 1 -3.078994 -0.647627 2.178957 1 -0.172643 -4.435350 2.793928 1 -2.152766 -2.942612 2.469667 1 2.135480 -3.525800 2.539514 1 -2.827205 1.624922 1.276154 1 1.128123 4.409964 0.698343 6 -1.384932 3.930419 0.345733 8 -1.228174 5.148179 0.432748 8 -2.553072 3.406250 -0.151658 1 -3.124443 4.178094 -0.351662 7 1.961800 2.517128 0.935690 1 2.896107 2.916299 0.999085 1 3.919624 0.823461 1.502392 1 -0.765748 1.088781 -0.404168 6 2.927916 0.364772 1.538960 8 0.078554 -2.717022 -1.370508 6 -1.829537 -1.375140 -1.516744 6 -2.583012 -2.402151 -0.939161 6 -2.429532 -0.198198 -1.983126 6 -3.964952 -2.235824 -0.806146 6 -3.812280 -0.047606 -1.846237 100 Page 119 of 223 Dalton Transactions 6 -4.581478 -1.059383 -1.253357 1 -2.078866 -3.301239 -0.586310 1 -1.819552 0.581845 -2.437465 1 -4.558960 -3.027222 -0.343662 1 -4.288065 0.868346 -2.203435 1 -5.660809 -0.931154 -1.142885 7 -0.372258 -1.558395 -1.582306 6 1.686566 -0.457477 -1.854160 6 2.201707 0.851665 -2.038380 6 2.598904 -1.535181 -1.705996 6 3.573940 1.086125 -2.062794 6 3.974405 -1.283019 -1.738754 6 4.470388 0.016106 -1.911044 1 1.490973 1.674408 -2.144686 1 2.227216 -2.545850 -1.566496 1 3.947438 2.104363 -2.195269 1 4.668673 -2.119066 -1.621946 1 5.548205 0.195115 -1.927900 7 0.290502 -0.476812 -1.827288 101 Dalton Transactions Page 120 of 223 (Transition state) Charge = 0 Multiplicity = 1 Sum of electronic and thermal Free Energies= -1467.818093 6 -3.781163 0.115700 2.044601 6 -3.351849 1.282318 1.386600 6 -1.998058 1.459739 1.060172 6 -1.043779 0.464166 1.457239 6 -1.489106 -0.719006 2.137259 6 -2.875691 -0.879265 2.399733 6 -1.525060 2.613169 0.337125 6 0.341169 0.653392 1.181642 6 0.789226 1.748404 0.285606 6 -0.207340 2.776080 0.009908 6 2.260002 2.033933 0.355358 6 3.083409 1.096874 0.933878 6 1.259037 -0.293872 1.668336 6 -0.521205 -1.692021 2.521500 1 -0.861205 -2.607468 3.012191 1 -2.254562 3.378142 0.057413 1 -4.843212 -0.015779 2.267535 1 -4.071561 2.052465 1.098146 1 -3.214421 -1.789691 2.901294 1 0.107810 3.660510 -0.541222 1 4.164769 1.231948 0.944535 6 2.973292 3.157056 -0.272900 8 4.161236 3.425686 -0.103488 8 2.200365 3.893794 -1.126438 1 2.787306 4.597714 -1.477827 7 2.620010 -0.051484 1.485858 1 3.286538 -0.729139 1.853242 1 1.576285 -2.196335 2.649694 1 0.665342 1.009130 -0.849409 6 0.828203 -1.469680 2.322643 8 0.584006 0.178373 -1.784603 6 1.410070 -1.903739 -1.065796 102 Page 121 of 223 Dalton Transactions 6 2.716678 -1.408996 -1.209424 6 1.191685 -3.241345 -0.680520 6 3.803502 -2.252635 -0.956641 6 2.288855 -4.067176 -0.429623 6 3.599550 -3.580858 -0.562463 1 2.871966 -0.374455 -1.513186 1 0.172287 -3.610970 -0.580780 1 4.817167 -1.859971 -1.066812 1 2.116498 -5.103511 -0.128936 1 4.452046 -4.234053 -0.362819 7 0.299009 -1.033085 -1.324462 6 -2.055167 -0.823577 -1.402903 6 -3.231909 -1.514165 -0.979118 6 -2.219935 0.425377 -2.078077 6 -4.497203 -0.980761 -1.190037 6 -3.501146 0.940438 -2.282395 6 -4.643905 0.262654 -1.831012 1 -3.105572 -2.473979 -0.473029 1 -1.352375 0.972323 -2.433835 1 -5.378237 -1.526712 -0.842681 1 -3.607020 1.899885 -2.796378 1 -5.637325 0.689186 -1.989608 7 -0.900498 -1.510473 -1.100744 103 Dalton Transactions Page 122 of 223 Charge = 0 Multiplicity = 1 Sum of electronic and thermal Free Energies= -1467.827425 6 3.882558 -0.546183 1.773427 6 3.415421 -1.659540 1.080365 6 2.029307 -1.795712 0.797546 6 1.114911 -0.805335 1.283408 6 1.614199 0.354529 1.965368 6 3.006981 0.470236 2.182866 6 1.505355 -2.864529 0.021426 6 -0.288592 -0.964812 1.063316 6 -0.802381 -2.091333 0.321533 6 0.144944 -3.008264 -0.208924 6 -2.260616 -2.202662 0.202192 6 -3.043630 -1.187630 0.722451 6 -1.159583 0.061477 1.537416 6 0.692873 1.369667 2.359263 1 1.080723 2.270785 2.840432 1 2.201563 -3.599343 -0.391791 1 4.952550 -0.442826 1.971452 1 4.103714 -2.432140 0.729332 1 3.387969 1.355646 2.697721 1 -0.208462 -3.849723 -0.799835 1 -4.129501 -1.216835 0.639359 6 -3.045507 -3.287026 -0.428238 8 -4.270670 -3.294037 -0.519499 8 -2.298262 -4.317327 -0.912759 1 -2.938437 -4.957378 -1.293298 7 -2.522750 -0.110708 1.341666 1 -3.153272 0.626923 1.658748 1 -1.378092 1.980121 2.498710 1 -0.542811 -0.581037 -1.127528 6 -0.670447 1.211067 2.181042 8 -0.663198 0.177222 -1.756323 6 -1.455550 2.183892 -0.768980 104 Page 123 of 223 Dalton Transactions 6 -2.772709 1.732787 -1.006176 6 -1.243111 3.488093 -0.260520 6 -3.853983 2.571154 -0.718623 6 -2.338781 4.305226 0.020091 6 -3.652183 3.857152 -0.198283 1 -2.937405 0.738030 -1.417351 1 -0.224237 3.833839 -0.091515 1 -4.867405 2.207762 -0.907677 1 -2.161591 5.309952 0.412844 1 -4.503006 4.504221 0.026255 7 -0.357954 1.333027 -0.992051 6 2.008404 1.146691 -1.182426 6 3.201166 1.756379 -0.667665 6 2.176663 0.012191 -2.047055 6 4.463557 1.273425 -0.990795 6 3.452957 -0.455493 -2.350403 6 4.607407 0.147903 -1.820227 1 3.087987 2.626734 -0.017616 1 1.312501 -0.472714 -2.491752 1 5.347302 1.764240 -0.573727 1 3.549667 -1.320266 -3.013399 1 5.598858 -0.239220 -2.066528 7 0.866512 1.767148 -0.771697 105 Dalton Transactions Page 124 of 223 2.5.PBE-D2 Optimized geometries associated with the Inorganic Catalyst: Ru-CF 2.5.1. Adsorption energies of the different reagents energy(sigma->0) = -802.92727762 H 88 Ru 57 1.00000000000000 25.0000000000000000 0.0000000000000000 0.0000000000000000 0.0000000000000000 25.0000000000000000 0.0000000000000000 0.0000000000000000 0.0000000000000000 25.0000000000000000 H Ru 88 57 Direct 0.5528452298544688 0.7193158900720705 0.4988039763595636 0.4919664668746489 0.7545516563876662 0.4566448364547648 0.4143621078283493 0.7231358065397163 0.4823303392420863 0.3246353776829808 0.6701712400729040 0.4891105686804098 0.2441059146986728 0.6377349637674176 0.4758018934299579 0.2457786447590602 0.6376122308788509 0.5124561855028500 0.2852054799296551 0.5555978206904952 0.6273199146349889 0.2714116135462563 0.5311261759530692 0.6072668232337851 0.3467085081582549 0.5487416960610435 0.6947918739120036 0.3673193529612535 0.5953677054027696 0.6215306603657682 0.4306479864747679 0.5882195676536573 0.7046225320186136 0.5456987885156213 0.5809278623801658 0.7075031763690313 0.5578110202109094 0.7014900313596033 0.6103247951757949 0.5299153120330555 0.6979890191404751 0.6284505765518785 0.4549698752100614 0.6661188702407609 0.5941087182910110 0.3038075020570391 0.6084937177356041 0.5612863960451336 0.5925226784541747 0.4943888176536463 0.7007448129099990 0.6272471891808843 0.5671575219658919 0.7022919670332651 0.5969416610424192 0.6154144759747256 0.6397316378122125 0.6657020529412495 0.6292159316388605 0.6018489645446148 0.6794021415983816 0.6111772098883507 0.5394227216003814 0.7273118054347369 0.6281381809906857 0.4745567684438792 0.6126919993949246 0.6703778648767607 0.5495671282233264 0.6541896142592133 0.6620589951131720 0.4730956064439860 0.6822832208472496 0.6027121938172858 0.4035251103860747 0.6208181817720243 0.5968207816208061 0.3273918463464978 106 Page 125 of 223 Dalton Transactions 0.6331604990370491 0.5454120735360117 0.2661926234966875 0.6047078990330146 0.5556813694261264 0.2463769105373642 0.5121394595398504 0.7193362626072504 0.3856508993832998 0.5810345354541503 0.6808912335088307 0.4171830648102396 0.5206976410438913 0.6582263625278633 0.3353138162348857 0.5440894192549153 0.5959644109930976 0.2773031249063443 0.4519890601272390 0.5486528205583751 0.2740045866071905 0.3603790071861719 0.4934333858539196 0.2811570207430756 0.4142914912982862 0.6153700025387232 0.3327276192080462 0.4479164616234454 0.6710172292575373 0.3893464026450719 0.2947363563199509 0.6065771023275578 0.4220110217145469 0.2561360438615889 0.5504723511416617 0.4955729705680806 0.2766896344480308 0.4943705290297692 0.4244863018393003 0.2611235092447791 0.3381951535534898 0.4797964312208378 0.3268389937696998 0.5662294354537178 0.3396609375944530 0.2505661696107410 0.3952548434522208 0.5130262898526355 0.2679737511499731 0.4014822109117559 0.4308248758569824 0.3240448849656967 0.4238399965882709 0.3331470809666624 0.4104228924868138 0.3681179113284868 0.3255788883102104 0.3623202571046441 0.4130202956100293 0.2634609605531446 0.4686114241517172 0.3540815947623415 0.2587529450849750 0.5426043174850346 0.3787416463683054 0.2828676509071639 0.4171806194246810 0.2612000587667226 0.4881989190220421 0.3328021717225803 0.3340644643990463 0.5235042289917907 0.4913771152373343 0.2317743745474150 0.5204267274735889 0.5554986679767080 0.2674037780654610 0.4882838403173638 0.5361782359460141 0.2654097717724107 0.3843548684934747 0.5608797955157816 0.2858790338031942 0.3688025727347933 0.4910198464374878 0.3184187028337117 0.3332698923009137 0.3420475604840563 0.3384871706959780 0.4407133773474754 0.6152923280615310 0.4057781184362034 0.2623907460019271 0.6362454912750771 0.4291167901656925 0.2776097211974199 0.4522671986122600 0.4373400657992462 0.2725860661741470 0.5460864037710320 0.4942335096433145 0.2693711814651129 0.3363921278252161 0.4624464654556060 0.6395261547386589 0.3961401462314986 0.4913768061210299 0.7075110253813405 0.4389391426865438 0.3973950552857021 0.7023218151983142 0.5263719616043309 0.3337403184833654 0.6788946893334057 0.4943619243609936 0.5062742510394265 0.7267072663602231 0.4890160224141581 0.4727289484292554 0.7262459768193053 0.5965680024591500 0.3717889168650163 0.6367608990676430 0.5382640400703091 0.4049100301424892 0.7035032568899715 0.6661713896573919 0.3472278959042137 0.5934499326637339 0.6467029242406954 0.3243337828083507 0.5755727796495081 0.6419410356696018 0.5458076408826267 0.6168832559062277 0.6443659902969984 0.4408557191368394 0.6123008717414370 0.7226124423760829 0.5457276813988339 0.4717208155668821 107 Dalton Transactions Page 126 of 223 0.7182617771362751 0.5050474329527105 0.5486541672253822 0.7243593655929728 0.4470962491020537 0.4902215891558919 0.7057922678495301 0.3677208266841435 0.5177009778548201 0.6116019603971853 0.2827986673047481 0.4432025922657100 0.6556711476563899 0.3306036413504502 0.4702632303753556 0.5622444980631350 0.2766867129873671 0.5872213909177716 0.5339198423455360 0.2732041405889814 0.6053519998988129 0.2787231944718289 0.4094753369970193 0.6037914997623224 0.2653478301230215 0.4380687555357127 0.5858165240229458 0.4620518570755392 0.3306006358705401 0.6107479043713490 0.3649392019528252 0.3834061472475416 0.6105544807716142 0.6293562300357056 0.3329418914133029 0.3575348602513587 0.6500446755155442 0.3603844318922066 0.3487481211588283 0.6601145906948288 0.4360125170791753 0.3998060312377487 0.6274855716404407 0.4923447622830400 0.3297132403636501 0.4241494237606716 0.4949684009319366 0.4033256240381024 0.4856261254842379 0.4922112171830769 0.3147829179144060 0.5188294472653271 0.4417199197536970 0.4004651242155092 0.5745089867113805 0.4352880887977146 0.3114633019586001 0.4235454283940441 0.6022692291562487 0.4073190638159837 0.4842731359446429 0.5970378819339065 0.3178903133043010 0.5172471727069251 0.5468551305554440 0.3995859036733314 0.5795846037441946 0.5449100448171661 0.3091848177319621 0.6119183461438445 0.4938171941711095 0.4009458519878123 0.5131950302622150 0.6580464724546221 0.4040426513534097 0.6039957148429459 0.6027562648763588 0.3979658119692590 0.4257431263061832 0.4919060881863814 0.5721534194528471 0.4890545272573271 0.4932334709213689 0.4877043447439321 0.5231107659314338 0.4355863584791411 0.5720206979395248 0.5788097671767348 0.4402344993361639 0.4835427913393750 0.4271509107084662 0.6010157640894691 0.5734583597073064 0.4890914443894241 0.5997055951160712 0.4886922118936043 0.5199619090320683 0.5480776078582139 0.5697921286951245 0.5778363109820187 0.5472180762998734 0.4841259036142738 0.6113667197248943 0.4938983658547701 0.5732074797503468 0.6760383431437336 0.4980602398196708 0.5008775908748145 0.4804639169553660 0.7039348110317051 0.4942215179024974 0.5201376924978061 0.6507117982903023 0.5734146400343382 0.5827878954659244 0.6572759037910978 0.4857884926759630 0.6165848702879354 0.6026924851126227 0.5706932564713830 0.6732600539979464 0.5941600908527420 0.4702649380121950 0.4916999784916741 0.4901964866872693 0.6574739595211548 0.5842491944471780 0.4363816200328258 0.6546975907365282 0.4885069601236747 0.5926533582595293 0.6582813513256467 0.5832467354862076 0.5493923794455671 0.6592576675310520 0.3342112091647244 0.4443803350935462 0.4035858418903364 0.3881741115694397 0.4392212789840704 0.3157339246716748 108 Page 127 of 223 Dalton Transactions 0.3343121969321828 0.5457829085783129 0.4069447887927198 0.3919109002696113 0.5449815619232667 0.3206824106650341 0.2986971057098973 0.4929037592706621 0.4918280284465255 0.3332294834139795 0.4388031082148705 0.5732595875770586 0.3962318777020799 0.4402797077385619 0.4877007925255878 0.3017561792386241 0.6046581195831664 0.4913234398753651 0.3340572700514442 0.5451175436217772 0.5767094210179181 0.3926475688924014 0.5457042311280148 0.4914864745337917 0.3944354926770676 0.6533876591690102 0.4861577768211073 0.4008387300977347 0.4355397597684436 0.6576961568031777 0.4009014029854843 0.5424699089120052 0.6606376107017891 0.4249794770748004 0.3872697727005329 0.4029582340164720 0.4794184835751416 0.3845738645448876 0.3138290853330069 0.5170549825832870 0.3308392444030502 0.3985529081835835 0.6059170948537770 0.3864641148743353 0.3958034134462969 0.4823203867411400 0.2823235712685128 0.4811513821168125 0.4279776213637102 0.3849856302372628 0.5711967896471325 0.4896907810408396 0.3868589367731674 0.4845612774043214 0.5218334205194434 0.3321416114912757 0.5649438874493179 0.5867891568311653 0.3277534059967582 0.4813112822728065 0.6142772674429705 0.3859772129171165 0.5640383694677654 0.6733859448635641 0.4016194773424500 0.4742172852486556 0.4929013338703559 0.3834142388765088 0.6550895450817197 0.3060563373945449 0.3841898895050570 0.4821893836864835 0.3986040166488615 0.3330535536054058 0.4873742346156350 109 Dalton Transactions Page 128 of 223 energy(sigma->0) = -48.00691281 H1 C2 O2 F3 1.00000000000000 25.0000000000000000 0.0000000000000000 0.0000000000000000 0.0000000000000000 25.0000000000000000 0.0000000000000000 0.0000000000000000 0.0000000000000000 25.0000000000000000 H C O F 1 2 2 3 Direct 0.5917318129753645 0.6454038775313128 0.2849535427366042 0.6412560196093282 0.7621857248694578 0.3122700095831328 0.6276842060866759 0.7020959774938634 0.3214630571504984 0.6391393559477195 0.6791019043705844 0.3627110150834899 0.6019569370789227 0.6829767510555350 0.2791610136900871 0.6752557189292859 0.7802252921097891 0.3502312599670994 0.5956447490775238 0.7920669660276860 0.3148489076400013 0.6640492002951872 0.7708719065417790 0.2636279941490897 110 Page 129 of 223 Dalton Transactions energy(sigma->0) = -65.56576519 H 9 O 4 Cl 1 1.00000000000000 25.0000000000000000 0.0000000000000000 0.0000000000000000 0.0000000000000000 25.0000000000000000 0.0000000000000000 0.0000000000000000 0.0000000000000000 25.0000000000000000 H O Cl 9 4 1 Direct 0.9465747995529601 0.2792783683698929 0.1335062309989899 0.0100887688715582 0.3001698092476405 0.1498434773059441 0.9979316599933332 0.2356808309448935 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