Thermodynamic Hydricity Research Articles

Linear Free Energy Relationships Associated with Hydride Transfer From [(6,6'-R2-bpy)Re(CO)3H]: A Cautionary Tale in Identifying Hydrogen Bonding Effects in the Secondary Coordination Sphere.

Six rhenium hydride complexes, [(6,6'-R2-bpy)Re(CO)3H] (bpy = 2,2'-bipyridine, R = OEt, OMe, NHMe, Me, F, Br), were synthesized. These complexes insert CO2 to form rhenium formate complexes of the type [(6,6'-R2-bpy)Re(CO)3{OC(O)H}]. All the rhenium formate species were characterized using X-ray crystallography, which revealed that the bpy ligand is not coplanar with the metal coordination plane containing the two nitrogen donors of the bpy ligand but tilted. A solid-state structure of [(6,6'-Me2-bpy)Re(CO)3H] determined using MicroED also featured a tilted bpy ligand. The kinetics of CO2 insertion into complexes of the type [(6,6'-R2-bpy)Re(CO)3H] were measured experimentally and the thermodynamic hydricities of [(6,6'-R2-bpy)Re(CO)3H] species were determined using theoretical calculations. A Brønsted plot constructed using the experimentally determined rate constants for CO2 insertion and the calculated thermodynamic hydricities for [(6,6'-R2-bpy)Re(CO)3H] revealed a linear free energy relationship (LFER) between thermodynamic and kinetic hydricity. This LFER is different to the previously determined relationship for CO2 insertion into complexes of the type [(4,4'-R2-bpy)Re(CO)3H]. At a given thermodynamic hydricity, CO2 insertion is faster for complexes containing a 6,6'-substituted bpy ligand. This is likely in part due to the tilting observed for systems with 6,6'-substituted bpy ligands. Notably, the 6,6'-(NHMe)2-bpy ligand could in principle stabilize the transition state for CO2 insertion via hydrogen bonding. This work shows that if only the rate of CO2 insertion into [(6,6'-(NHMe)2-bpy)Re(CO)3H] is compared to [(4,4'-R2-bpy)Re(CO)3H] systems, the increase in rate could be easily attributed to hydrogen bonding, but in fact all 6,6'-substituted systems lead to faster than expected rates.

Stepwise Reduction of Redox Noninnocent Nitrosobenzene to Aniline via a Rare Phenylhydroxylamino Intermediate on a Thiolate-Bridged Dicobalt Scaffold.

Nitrosobenzene (PhNO) and phenylhydroxylamine (PhNHOH) are of paramount importance because of their involvement as crucial intermediates in the biological metabolism and catalytic transformation of nitrobenzene (PhNO2) to aniline (PhNH2). However, a complete reductive transformation cycle of PhNO to PhNH2 via the PhNHOH intermediate has not been reported yet. In this context, we design and construct a new thiolate-bridged dicobalt scaffold that can accomplish coordination activation and reductive transformation of PhNO. Notably, an unprecedented reversible ligand-based redox sequence PhNO0 ↔ PhNO•- ↔ PhNO2- can be achieved on this well-defined {CoIII(μ-SPh)2CoIII} functional platform. Further detailed reactivity investigations demonstrate that the PhNO0 and PhNO•- complexes cannot react with the usual hydrogen and hydride donors to afford the corresponding phenylhydroxylamino (PhNHO-) species. However, the double reduced PhNO2- complex can readily undergo N-protonation with an uncommon weak proton donor PhSH to selectively yield a stable dicobalt PhNHO- bridged complex with a high pKa value of 13-16. Cyclic voltammetry shows that there are two successive reduction events at E1/2 = -0.075 V and Ep = -1.08 V for the PhNO0 complex, which allows us to determine both bond dissociation energy (BDEN-H) of 59-63 kcal·mol-1 and thermodynamic hydricity (ΔGH-) of 71-75 kcal·mol-1 of the PhNHO- complex. Both values indicate that the PhNO•- complex is not a potent hydrogen abstractor and the PhNO0 complex is not an efficient hydride acceptor. In the presence of BH3 as a combination of protons and electrons, facile N-O bond cleavage of the coordinated PhNHO- group can be realized to generate PhNH2 and a dicobalt hydroxide-bridged complex. Overall, we present the first stepwise reductive sequence, PhNO0 ↔ PhNO•- ↔ PhNO2- ↔ PhNHO- → PhNH2.

Thermodynamic and Kinetic Activity Descriptors for the Catalytic Hydrogenation of Ketones.

Activity descriptors are a powerful tool for the design of catalysts that can efficiently utilize H2 with minimal energy losses. In this study, we develop the use of hydricity and H- self-exchange rates as thermodynamic and kinetic descriptors for the hydrogenation of ketones by molecular catalysts. Two complexes with known hydricity, HRh(dmpe)2 and HCo(dmpe)2, were investigated for the catalytic hydrogenation of ketones under mild conditions (1.5 atm and 25 °C). The rhodium catalyst proved to be an efficient catalyst for a wide range of ketones, whereas the cobalt catalyst could only hydrogenate electron-deficient ketones. Using a combination of experiment and electronic structure theory, thermodynamic hydricity values were established for 46 alkoxide/ketone pairs in both acetonitrile and tetrahydrofuran solvents. Through comparison of the hydricities of the catalysts and substrates, it was determined that catalysis was observed only for catalyst/ketone pairs with an exergonic H- transfer step. Mechanistic studies revealed that H- transfer was the rate-limiting step for catalysis, allowing for the experimental and computation construction of linear free-energy relationships (LFERs) for H- transfer. Further analysis revealed that the LFERs could be reproduced using Marcus theory, in which the H- self-exchange rates for the HRh/Rh+ and ketone/alkoxide pairs were used to predict the experimentally measured catalytic barriers within 2 kcal mol-1. These studies significantly expand the scope of catalytic reactions that can be analyzed with a thermodynamic hydricity descriptor and firmly establish Marcus theory as a valid approach to develop kinetic descriptors for designing catalysts for H- transfer reactions.

Hydrogen Reduction Reduction (HRR)

The year 2023 marks the bicentennial of the discovery of heterogeneous H2 catalysis. Nowadays, the hydrogen oxidation reaction (HOR), which converts H2 to protons (H+), is one of the most important transformations in energy research. Meanwhile, hydrogenation reactions, which transfer net H-atoms (H·) to organic substrates from H2, play pivotal roles in various chemical industries. In comparison, it is surprising to see that a heterogenous catalytic reaction that directly converts H2 to hydrides (H–) still remains elusive. Hydride transfer is a critical elementary reaction step that spans biological catalysis, organic synthesis and energy conversion. Conventionally, hydride transfer reactions are performed using (bio)molecular hydride reagents under homogeneous conditions. Here we report a conceptually distinct heterogeneous hydride transfer reaction via the net electrocatalytic hydrogen reduction reaction (HRR), which reduces H2 to hydrides. The reaction proceeds by H2 dissociative adsorption on a metal electrode to form surface M−H species, which are then negatively polarized to drive hydride transfer to molecular hydride acceptors with up to 91% Faradaic efficiency. The hydride transfer reactivity of surface M−H species is highly tunable, and, depending on the electrode potential, the thermodynamic hydricity of Pt−H on the same Pt electrode can continuously span a range of >40 kcal/mol.In addition to this electrochemical transformation, we further developed an alternative strategy to achieve heterogeneous hydride transfer on dispersed metal catalysts under non-electrochemical conditions. In the presence of a base, deprotonation of surface M-H builds up electron density at the metal surface and thereby causes spontaneous polarization which can then drive hydride transfer from metal nanoparticles. Based on this, HRR can be performed under standard hydrogenation conditions with the addition of a base using dispersed metal catalysts, and the surface hydricity is now controlled by the solution basicity. We further demonstrate that this non-electrochemical HRR method can be applied to NADH regeneration which is closely related to industrial biocatalysis. The discovery of HRR reveals the fundamental hydride transfer reactivity of surface M-H species as well as its polarization-dependent nature. Both the electrochemical and non-electrochemical HRR methods establish sustainable strategies for accessing reactive hydrides directly from H2. Figure 1

Carbon Dioxide Insertion into Rhenium Hydrides as a Probe for the Impact of Solvent on Linear Free Energy Relationships between Thermodynamic and Kinetic Hydricity

Carbon Dioxide Insertion into Rhenium Hydrides as a Probe for the Impact of Solvent on Linear Free Energy Relationships between Thermodynamic and Kinetic Hydricity

Synthesis, Structural Characterization, and CO2 Reactivity of a Constitutionally Analogous Series of Tricopper Mono-, Di-, and Trihydrides.

The formation of hydrides at heterogeneous copper surfaces results in dramatic structural and reactivity changes, yet the morphologies of these materials and their respective roles in catalysis are not well understood. Of particular interest is the reactivity of heterogeneous copper hydrides with carbon dioxide (CO2), an early mechanistic branching point in the CO2 reduction reaction. Herein, we report the synthesis, characterization, and reactivity of tricopper compounds supported by a facially biased, chelating tris(carbene) ligand scaffold. This sterically bulky environment affords access to an isolable series of tricopper hydrides: [LCu3H]2+ (4), [LCu3H2]+ (3), and LCu3H3 (6). Single-crystal X-ray diffraction and solution NMR spectroscopy studies reveal both geometric flexibility within the Cu3 core and fluxionality of hydride ligands across the Cu3 cluster, providing both atomically precise experimental analogues of static surface species and emulating dynamic ligand behavior proposed for surfaces. Electronic structure calculations serve as a predictor of hydricity, which was likewise benchmarked experimentally via both protonolysis and hydride abstraction reactions. Increased hydride number (and commensurately lower cluster charge) results in more hydridic complexes, with a thermodynamic hydricity range spanning >30 kcal/mol. These thermochemical studies serve as an accurate predictor of CO2 reactivity. Together, this Cu3Hx series exhibits the structure/reactivity relationships proposed for catalytically active copper surfaces, validating the application of carefully designed molecular clusters toward elucidating mechanisms in surface science.

When 3+1 is Less Than 2+2: Surprisingly Moderate Hydricities in Heteroleptic Rhodium Complexes Containing Triphosphine and Monophosphine Ligands

Rhodium(I) complexes with the formula [Rh(PP2)(PR3)]+ (PP2 = PhP(CH2CH2PPh2)2; R = Ph, Et, or Me) were synthesized and characterized. Their reactions with H2 in the presence of strong bases, forming rhodium(I) hydrides with the formula HRh(PP2)(PR3), were studied, and the structure of HRh(PP2)(PPh3) was determined by X-ray crystallography. These are the first structurally characterized rhodium complexes with this combination of triphosphine and monophosphine ligands. Their thermodynamic hydricities were determined from the equilibrium constants of their heterolytic H2 activation equilibria. The values of ΔG°H– range from 37.3 kcal/mol for HRh(PP2)(PMe3) to 42.4 kcal/mol for HRh(PP2)(PPh3) in MeCN. These hydricities are surprisingly modest in comparison to their close analogues with the HRh(diphosphine)2 ligand framework, which are among the most powerful known hydride donors. Due to this decreased reactivity, the hydricities are in a nearly optimal range for CO2 hydrogenation, balancing the favorability of hydride transfer with the free energy for H2 activation. The structural factors underlying the thermodynamic trends, including the relatively small variation in hydricity imparted by the monophosphine and the higher overall ΔG°H– values compared to electronically similar bis(diphosphine) complexes, are largely attributable to the small bite angles within the chelate rings of the triphosphine ligand in these complexes.

Structure and Thermodynamic Hydricity in Cobalt(triphosphine)(monophosphine) Hydrides.

The mononuclear cobalt hydride complex [HCo(triphos)(PMe3)], in which triphos = PhP(CH2CH2PPh2)2, was synthesized and characterized by X-ray crystallography and by 1H and 31P NMR spectroscopy. The geometry of the compound is a distorted trigonal bipyramid in which the axial positions are occupied by the hydride and the central phosphorus atom of the triphos ligand, while the PMe3 and terminal triphos donor atoms occupy the equatorial positions. Protonation of [HCo(triphos)(PMe3)] generates H2 and the Co(I) cation, [Co(triphos)(PMe3)]+, and this reaction is reversible under an atmosphere of H2 when the proton source is weakly acidic. The thermodynamic hydricity of HCo(triphos)(PMe3) was determined to be 40.3 kcal/mol in MeCN from measurements of these equilibria. The reactivity of the hydride is, therefore, well suited to CO2 hydrogenation catalysis. Density functional theory (DFT) calculations were performed to evaluate the structures and hydricities of a series of analogous cobalt(triphosphine)(monophosphine) hydrides where the phosphine substituents are systematically changed from Ph to Me. The calculated hydricities range from 38.5 to 47.7 kcal/mol. Surprisingly, the hydricities of the complexes are generally insensitive to substitution at the triphosphine ligand, as a result of competing structural and electronic trends. The DFT-calculated geometries of the [Co(triphos)(PMe3)]+ cations are more square planar when the triphosphine ligand possesses bulkier phenyl groups and more tetrahedrally distorted when the triphosphine ligand has smaller methyl substituents, reversing the trend observed for [M(diphosphine)2]+ cations. More distorted structures are associated with an increase in ΔGH-°, and this structural trend counteracts the electronic effect in which methyl substitution at the triphosphine is expected to yield smaller ΔGH-° values. However, the steric influence of the monophosphine follows the normal trend that phenyl substituents give more distorted structures and increased ΔGH-° values.

Benchmarking Density Functionals, Basis Sets, and Solvent Models in Predicting Thermodynamic Hydricities of Organic Hydrides.

Many renewable energy technologies, such as hydrogen gas synthesis and carbon dioxide reduction, rely on chemical reactions involving hydride anions (H-). When selecting molecules to be used in such applications, an important quantity to consider is the thermodynamic hydricity, which is the free energy required for a species to donate a hydride anion. Theoretical calculations of thermodynamic hydricity depend on several parameters, mainly the density functional, basis set, and solvent model. In order to assess the effects of the above three parameters, we carry out hydricity calculations with different combinations of density functionals, basis sets, and solvent models for a set of organic molecules with known experimental hydricity values. The data are analyzed by comparing the R2 and root-mean-squared error (RMSE) of linear fits with a fixed slope of 1 and using the Akaike Information Criterion to determine statistical significance of the RMSE rank ordering. Based on these results, we quantified the accuracy of theoretical predictions of hydricity and found that the best compromise between accuracy and computational cost was obtained by using the B3LYP-D3 density functional for the geometry optimization and free-energy corrections, either ωB97X-D3 or M06-2X-D3 for single-point energy corrections, combined with a basis set no larger than def-TZVP and the C-PCM ISWIG solvation model. At this level of theory, the RMSEs of hydricity calculations for organic molecules in acetonitrile and dimethyl sulfoxide were found to be <4 and <10 kcal/mol, respectively, for an experimental data set with a dynamic range of 20-150 kcal/mol.

Correlating Thermodynamic and Kinetic Hydricities of Rhenium Hydrides.

The kinetics of hydride transfer from Re(Rbpy)(CO)3H (bpy = 4,4'-R-2,2'-bipyridine; R = OMe, tBu, Me, H, Br, COOMe, CF3) to CO2 and seven different cationic N-heterocycles were determined. Additionally, the thermodynamic hydricities of complexes of the type Re(Rbpy)(CO)3H were established primarily using computational methods. Linear free-energy relationships (LFERs) derived by correlating thermodynamic and kinetic hydricities indicate that, in general, the rate of hydride transfer increases as the thermodynamic driving force for the reaction increases. Kinetic isotope effects range from inverse for hydride transfer reactions with a small driving force to normal for reactions with a large driving force. Hammett analysis indicates that hydride transfer reactions with greater thermodynamic driving force are less sensitive to changes in the electronic properties of the metal hydride, presumably because there is less buildup of charge in the increasingly early transition state. Bronsted α values were obtained for a range of hydride transfer reactions and along with DFT calculations suggest the reactions are concerted, which enables the use of Marcus theory to analyze hydride transfer reactions involving transition metal hydrides. It is notable, however, that even slight perturbations in the steric properties of the Re hydride or the hydride acceptor result in large deviations in the predicted rate of hydride transfer based on thermodynamic driving forces. This indicates that thermodynamic considerations alone cannot be used to predict the rate of hydride transfer, which has implications for catalyst design.

Biomimetic Metal-Free Hydride Donor Catalysts for CO2 Reduction

The catalytic reduction of carbon dioxide to fuels and value-added chemicals is of significance for the development of carbon recycling technologies. One of the main challenges associated with catalytic CO2 reduction is product selectivity: the formation of carbon monoxide, molecular hydrogen, formate, methanol, and other products occurs with similar thermodynamic driving forces, making it difficult to selectively reduce CO2 to the target product. Significant scientific effort has been aimed at the development of catalysts that can suppress the undesired hydrogen evolution reaction and direct the reaction toward the selective formation of the desired products, which are easy to handle and store. Inspired by natural photosynthesis, where the CO2 reduction is achieved using NADPH cofactors in the Calvin cycle, we explore biomimetic metal-free hydride donors as catalysts for the selective reduction of CO2 to formate. Here, we outline our recent findings on the thermodynamic and kinetic parameters that control the hydride transfer from metal-free hydrides to CO2. By experimentally measuring and theoretically calculating the thermodynamic hydricities of a range of metal-free hydride donors, we derive structural and electronic factors that affect their hydride-donating abilities. Two dominant factors that contribute to the stronger hydride donors are identified to be (i) the stabilization of the positive charge formed upon HT via aromatization or by the presence of electron-donating groups and (ii) the destabilization of hydride donors through the anomeric effect or in the presence of significant structural constrains in the hydride molecule. Hydride donors with appropriate thermodynamic hydricities were reacted with CO2, and the formation of the formate ion (the first reduction step in CO2 reduction to methanol) was confirmed experimentally, providing an important proof of principle that organocatalytic CO2 reduction is feasible. The kinetics of hydride transfer to CO2 were found to be slow, and the sluggish kinetics were assigned in part to the large self-exchange reorganization energy associated with the organic hydrides in the DMSO solvent. Finally, we outline our approaches to the closure of the catalytic cycle via the electrochemical and photochemical regeneration of the hydride (R-H) from the conjugate hydride acceptors (R+). We illustrate how proton-coupled electron transfer can be efficiently utilized not only to lower the electrochemical potential at which the hydride regeneration takes place but also to suppress the unwanted dimerization that neutral radical intermediates tend to undergo. Overall, this account provides a summary of important milestones achieved in organocatalytic CO2 reduction and provides insights into the future research directions needed for the discovery of inexpensive catalysts for carbon recycling.

Toggling the Z-type interaction off-on in nickel-boron dihydrogen and anionic hydride complexes.

Completing a series of nickel-group 13 complexes, a coordinatively unsaturated nickel-boron complex and its derivatives with a H2, N2, or hydride ligand were synthesized and characterized. The toggling "on" of a Ni(0)-B(III) inverse-dative bond enabled the stabilization of a nickel-bound anionic hydride with a remarkably low thermodynamic hydricity of kcal mol-1 in THF. The flexible topology of the boron metalloligand confers both favorable hydrogen binding affinity and strong hydride donicity, albeit at the cost of high H2 basicity during deprotonation to form the hydride.

Frontispiece: Emerging Implications of the Concept of Hydricity in Energy‐Relevant Catalytic Processes

Thermodynamic hydricity of transition-metal hydrides is a key parameter to guide in framing new catalyst design concepts for several hydride transfer catalysis including energy-relevant processes such as H+ and CO2 reduction to H2 and formate, respectively. Important aspects of this emerging research direction are summarized in the Minireview by J. Choudhury et al. on page 5842.

Correction to “Thermodynamic Hydricity across Solvents: Subtle Electronic Effects and Striking Ligation Effects in Iridium Hydrides”

Correction to “Thermodynamic Hydricity across Solvents: Subtle Electronic Effects and Striking Ligation Effects in Iridium Hydrides”

Thermodynamic Hydricity of Small Borane Clusters and Polyhedral closo-Boranes.

Thermodynamic hydricity (HDAMeCN) determined as Gibbs free energy (ΔG°[H]−) of the H− detachment reaction in acetonitrile (MeCN) was assessed for 144 small borane clusters (up to 5 boron atoms), polyhedral closo-boranes dianions [BnHn]2−, and their lithium salts Li2[BnHn] (n = 5–17) by DFT method [M06/6-311++G(d,p)] taking into account non-specific solvent effect (SMD model). Thermodynamic hydricity values of diborane B2H6 (HDAMeCN = 82.1 kcal/mol) and its dianion [B2H6]2− (HDAMeCN = 40.9 kcal/mol for Li2[B2H6]) can be selected as border points for the range of borane clusters’ reactivity. Borane clusters with HDAMeCN below 41 kcal/mol are strong hydride donors capable of reducing CO2 (HDAMeCN = 44 kcal/mol for HCO2−), whereas those with HDAMeCN over 82 kcal/mol, predominately neutral boranes, are weak hydride donors and less prone to hydride transfer than to proton transfer (e.g., B2H6, B4H10, B5H11, etc.). The HDAMeCN values of closo-boranes are found to directly depend on the coordination number of the boron atom from which hydride detachment and stabilization of quasi-borinium cation takes place. In general, the larger the coordination number (CN) of a boron atom, the lower the value of HDAMeCN.

Thermodynamic and kinetic hydricity of transition metal hydrides.

The prevalence of transition metal-mediated hydride transfer reactions in chemical synthesis, catalysis, and biology has inspired the development of methods for characterizing the reactivity of transition metal hydride complexes. Thermodynamic hydricity represents the free energy required for heterolytic cleavage of the metal-hydride bond to release a free hydride ion, H-, as determined through equilibrium measurements and thermochemical cycles. Kinetic hydricity represents the rate of hydride transfer from one species to another, as measured through kinetic analysis. This tutorial review describes the common methods for experimental and computational determination of thermodynamic and kinetic hydricity, including advice on best practices and precautions to help avoid pitfalls. The influence of solvation on hydricity is emphasized, including opportunities and challenges arising from comparisons across several different solvents. Connections between thermodynamic and kinetic hydricity are discussed, and opportunities for utilizing these connections to rationally improve catalytic processes involving hydride transfer are highlighted.

Thermodynamic Hydricity across Solvents: Subtle Electronic Effects and Striking Ligation Effects in Iridium Hydrides

Insights into the influence of solvent on hydride transfer emerge from a study of iridium complexes with the formula [Cp*Ir(bpy-X)H]+ (bpy-X = 4,4′-X2-2,2′-bipyridine, X = H, Me, tBu, OMe, CO2Me, a...

Thermodynamic Hydricity of [FeFe]-Hydrogenases.

After remaining elusive for many years, terminal hydride states have now been identified in several native and mutant [FeFe]-hydrogenases. In this Perspective, hydride states of [FeFe]-hydrogenases are considered on the basis of hydricity, a thermodynamic parameter that has been instrumental for the rational design of synthetic molecular catalysts. Importantly, it is shown how the hydricity of [FeFe]-hydrogenases can inspire future research efforts in both the study of hydrogenases and the design of molecular catalysts. By using hydricity, quantitative linear free energy relationships can be developed to relate the driving force and rate of different [FeFe]-hydrogenase variants. Further development of these correlations across a wide range of hydrogenase variants can potentially lead to new insights into the structure-activity relationships of [FeFe]-hydrogenases. The hydricity of [FeFe]-hydrogenase is also compared to select transition metal hydride complexes, which emphasizes the strong electronic communication between the diiron active site and the extended protein scaffold of the enzyme. A mechanism is proposed for how key hydrogen bonding interactions might affect the hydricity of [FeFe]-hydrogenases, providing a basis for the emulation of these structural features in synthetic molecular complexes.

Thermodynamic Properties of Hydrogen-Producing Cobaloxime Catalysts: A Density Functional Theory Analysis.

Density functional theory calculations were carried out to study the electrochemical properties including reduction potentials, pKa values, and thermodynamic hydricities of three prototypical cobaloxime complexes, Co(dmgBF2)2 (dmgBF2 = difluoroboryl-dimethylglyoxime), Co(dmgH)2 (dmgH = dimethylglyoxime), and Co(dmgH)2(py)(Cl) (py = pyridine) in the acetonitrile (AN)–water solvent mixture. The electrochemical properties of Co(dmgBF2)2 in pure AN and pure water were also considered for comparison to reveal the key roles of the solvent on the catalytic reaction. In agreement with previous studies, hydrogen production pathways starting from reduction of the resting state of CoII and involving formation of the CoIIIH and CoIIH intermediates are the favorable ones for both bimetallic and monometallic pathways. However, we found that in pure AN, both the CoIIIH and CoIIH intermediates can react with a proton to produce H2. In the presence of water in the solvent, the reduction of CoIIIH to CoIIH is necessary for the reaction with a proton to occur to form H2. This suggests that it is possible to design catalytic systems by suitably tuning the composition of the AN–water mixture. We also identified the key role of axial coordination of the solvent molecules in affecting the catalytic reaction, which allows further catalyst design strategy. The highest hydride donor ability of Co(dmgH)2(py)(Cl) indicates that this complex displays the best catalytic hydrogen-producing performance among the three cobaloximes studied in this work.

Thermodynamic Hydricities of Biomimetic Organic Hydride Donors.

Thermodynamic hydricities (Δ GH-) in acetonitrile and dimethyl sulfoxide have been calculated and experimentally measured for several metal-free hydride donors: NADH analogs (BNAH, CN-BNAH, Me-MNAH, HEH), methylene tetrahydromethanopterin analogs (BIMH, CAFH), acridine derivatives (Ph-AcrH, Me2N-AcrH, T-AcrH, 4OH, 2OH, 3NH), and a triarylmethane derivative (6OH). The calculated hydricity values, obtained using density functional theory, showed a reasonably good match (within 3 kcal/mol) with the experimental values, obtained using "potential p Ka" and "hydride-transfer" methods. The hydride donor abilities of model compounds were in the 48.7-85.8 kcal/mol (acetonitrile) and 46.9-84.1 kcal/mol (DMSO) range, making them comparable to previously studied first-row transition metal hydride complexes. To evaluate the relevance of entropic contribution to the overall hydricity, Gibbs free energy differences (Δ GH-) obtained in this work were compared with the enthalpy (Δ HH-) values obtained by others. The results indicate that, even though Δ HH- values exhibit the same trends as Δ GH-, the differences between room-temperature Δ GH- and Δ HH- values range from 3 to 9 kcal/mol. This study also reports a new metal-free hydride donor, namely, an acridine-based compound 3NH, whose hydricity exceeds that of NaBH4. Collectively, this work gives a perspective of use metal-free hydride catalysts in fuel-forming and other reduction processes.