Hydrogen Transfer Step Research Articles

Cryogenic Rearrangements of Spiroheptadiyl: Light- or Heavy-Atom Quantum Tunneling?

Triplet 1,4-spiro[2.4]heptadiyl (SHD) has been shown experimentally to undergo rapid ring-opening and subsequent 1,2-hydrogen shift upon generation via photolysis of a diazene precursor at cryogenic temperatures. Modern computational tools elucidate the potential energy surface and kinetics behind this cascade reaction, disproving the earlier hypothesized mechanism invoking hot molecule effects in the first ring-opening step and tunneling in the second hydrogen transfer step. Instead, our results assign the SHD instability to heavy-atom tunneling and a subsequent photochemical hydrogen shift. This essentially is the opposite of the originally proposed mechanism. This case study thus addresses common misconceptions about the fundamental principles of tunneling involving hydrogen or carbon.

Asymmetric catalysis by chiral FLPs: A computational mini-review.

Steric hindrance in Lewis acid (LA) and Lewis base (LB) obstruct the Lewis acid-base adduct formation, and the pair was termed as frustrated Lewis pair (FLP). In the past 16years, the field of enantioselective catalysis by chiral FLPs has been slowly growing. It was shown that chiral LAs are significant as they are involved in the hydrogen transfer (HT) step to the imine, resulting in enantioselectivity. After H2 activation, the borohydride can exist in a number of plausible conformations and their stability is governed by the presence of noncovalent interaction through C-H····π and π····π interactions. However, LBs are not ideal for asymmetric induction as they compete with the imine substrate as a counter LB. Further, the proton transfer from chiral LB to the imine does not induce any chirality as chirality develops in the HT step. However, intramolecular FLPs with chiral scaffold are very efficient as they possess an optimum distance between LA and LB, which facilitates the H2 activation but precludes the adduct formation of the small molecules substrate with the LA component. This mini-review summarizes computational investigation involving chiral LA and LB, and discusses intramolecular FLPs in the enantioselective catalysis.

Cyclopentadienone Diphosphine Ruthenium Complex: A Designed Catalyst for the Hydrogenation of Carbon Dioxide to Methanol.

The development of homogeneous metal catalysts for the efficient hydrogenation of carbon dioxide (CO2) into methanol (CH3OH) remains a significant challenge. In this study, a new cyclopentadienone diphosphine ligand (CPDDP ligand) was designed, which could coordinate with ruthenium to form a Ru-CPDDP complex to efficiently catalyze the CO2-to-methanol process using dihydrogen (H2) as the hydrogen resource based on density functional theory (DFT) mechanistic investigation. This process consists of three catalytic cycles, stage I (the hydrogenation of CO2 to HCOOH), stage II (the hydrogenation of HCOOH to HCHO), and stage III (the hydrogenation of HCHO to CH3OH). The calculated free energy barriers for the hydrogen transfer (HT) steps of stage I, stage II, and stage III are 7.5, 14.5, and 3.5 kcal/mol, respectively. The most favorable pathway of the dihydrogen activation (DA) steps of three stages to regenerate catalytic species is proposed to be the formate-assisted DA step with a free energy barrier of 10.4 kcal/mol. The calculated results indicate that the designed Ru-CPDDP and Ru-CPDDPEt complexes could catalyze hydrogenation of CO2 to CH3OH (HCM) under mild conditions and that the transition-metal owning designed CPDDP ligand framework be one kind of promising potential efficient catalysts for HCM.

Influences of Ru and ZrO2 interaction on the hydroesterification of styrene.

Interfacial Lewis acid-base pairs are commonly found in ZrO2-supported metal catalysts due to the facile generation of oxygen vacancies of ZrO2. These pairs have been reported to play a crucial role in olefin hydroesterification, especially in the absence of acid promoters and ligands. In this study, a series of ZrO2-supported Ru catalysts with ruthenium(iii) chloride and ruthenium(iii) acetylacetonate as precursors were prepared for the styrene hydroesterification. The catalysts were thoroughly characterized by TPR, TEM, EPR, XPS, and FTIR. The Ru precursors significantly influenced the size and electronic properties of Ru clusters, albeit having minimal impact on oxygen vacancies. Mechanistic studies of styrene hydroesterification over ZrO2-supported Ru catalysts revealed that the carbon monoxide insertion followed the hydrogen transfer step to activated styrene. Higher activity is exhibited over ZrO2-supported Ru catalysts prepared with ruthenium(iii) chloride as a precursor, attributed to the lower adsorption strength of CO over Ru clusters, as evidenced by FTIR and DFT calculations.

Modelling kinetic isotope effects for Swern oxidation using DFT-based transition state theory

Kinetic isotope effects (KIEs) computed using DFT theory for the intramolecular hydrogen transfer step of the Swern oxidation compare well with experiment if basis sets of triple- or quadruple-ζ rather than double-ζ quality are used.

A nucleotide-copper(II) complex possessing a monooxygenase-like catalytic function.

The de novo design of artificial biocatalysts with enzyme-like active sites and catalytic functions has long been an attractive yet challenging goal. In this study, we present a nucleotide-Cu2+ complex, synthesized through a one-pot approach, capable of catalyzing ortho-hydroxylation reactions resembling those of minimalist monooxygenases. Both experimental and theoretical findings demonstrate that the catalyst, in which Cu2+ coordinates with both the nucleobase and phosphate moieties, forms a ternary-complex intermediate with H2O2 and tyramine substrates through multiple weak interactions. The subsequent electron transfer and hydrogen (or proton) transfer steps lead to the ortho-hydroxylation of tyramine, where the single copper center exhibits a similar function to natural dicopper sites. Moreover, Cu2+ bound to nucleotides or oligonucleotides exhibits thermophilic catalytic properties within the temperature range of 25 °C to 75 °C, while native enzymes are fully deactivated above 35 °C. This study may provide insights for the future design of oxidase-mimetic catalysts and serve as a guide for the design of primitive metallocentre-dependent enzymes.

Gold-Catalyzed Cyclization/Hydroboration of 1,6-Enynes: Synthesis of Bicyclo[3.1.0]hexane Boranes

The gold-catalyzed cyclization/hydroboration of 1,6-enynes offers facile, versatile, and atom-economical one-step access to bicyclo[3.1.0]hexane boranes. This new protocol proceeds in moderate to good yields under mild conditions. Different from bicyclo[3.1.0]hexane borates, these products are stable in air and during chromatography. Moreover, the borane moiety of the products can readily undergo a diverse array of transformations. The kinetic isotope effect experiment indicates that the hydrogen-transfer step is a fast process, which is not involved in the rate-limiting step.

A theoretical investigation on the hydrodesulphurisation mechanism of hydrogenated thiophene over Cu–Mo-modified FAU zeolite

ABSTRACT We have theoretically investigated the hydrodesulphurisation (HDS) mechanism of hydrogenated thiophene over Cu–Mo-modified FAU zeolite using a two-layer ONIOM (our Own N-layered Integrated molecular Orbital and molecular Mechanics) study. The thiophene is hydrogenated to 2,3-dihydrothiophene (2,3-DHT), 2,5-dihydrothiophene (2,5-DHT) and tetrahydrothiophene (THT) due to moderate free energy barriers. Hydrogenolysis desulphurisation (HYD) and concerted direct desulphurisation (DDS) are discussed. Ring-opening, hydrogen transfer and C−S bond cleavage steps of thiophene derivatives are involved in the HYD process. The rate-determining steps are the hydrogen transfer step for 2,5-DHT and C−S bond cracking step for 2,3-DHT and THT. The concerted DDS pathway is probably more favourable than the HYD pathway in the desulphurisation of 2,5-DHT. The difference charge density (DCD) analysis reveals that for the ring-opening process, the electrons are migrated from the organic chain to the Cu–Mo catalytic centre. The reduced density gradient (RDG) plots indicate that both steric hindrance and a weak van der Waals (VDW) interaction exist between organic fragment and catalytic centre for all transition states (TSs). The localised orbital locator (LOL) maps suggest that there are strong covalent interactions and weak VDW interactions between the atoms in the forming chemical bonds.

Catalyzed stereo-selective hydrogenation of ynamides to give enamines: Ethanol as a hydrogen donor

The reaction mechanism of the Pd(PPh3)4-catalyzed stereo-selective hydrogenation of ynamide to enamine with ethanol as a hydrogenation agent was investigated using density functional theory (DFT). The computational study provides the unique multistep hydrogenation pathway with the reasonable energy barrier, and the low energy barriers through the proton shuttle process are well rationalized. The calculation predicts that the ynamide undergoes stepwise hydrogenation by Pd-activated ethanol species, Pd(PPh3)4 acts as the precursor and the (EtOH)2-Pd-ynamide complex serves as active catalyst in the reaction. The calculation on the ynamide system indicates that there exist six competing reaction paths. For each path, the overall energy barrier is identified as the step corresponding to the oxidative addition of the O‒H bond of the hydrogenating agent to palladium center of the catalytic-complex. Ethanol could play as a proton shuttle in the hydrogen transfer step and therefore dramatically decreases the energy barrier for this concerned transition state, which is further validated by turnover frequency (TOF) model. The high selectivity towards enamine is attributed to the post-transition-state dynamics in the second hydrogenation stage, which leads exclusively to the dissociation of the product. The predominant product with E-configuration is reproduced theoretically, which is consistent with the experimental observation. Reduced density gradient (RDG) analysis and atoms in molecules (AIM) of the transition states confirm the significant influence of ethanol on the mechanism and stereo selectivity.

Theoretical description of the preferential hydrolytic deamination of cytosine over adenine

It has been shown experimentally that the hydrolytic deamination of cytosine in single-stranded DNA occurs significantly more frequently than that of adenine, despite similarities in their structure. To provide insight into this difference, we compute mechanisms for these reactions at the ωB97X-D/pcseg-2 level of theory, and we include quantum tunneling effects of nuclei. We calculate an activation energy of 117.9 kJ/mol for the deamination of cytosine in the presence of three water molecules, and we calculate 147.1 kJ/mol for the analogous process with adenine. The rate-determining step for both cytosine and adenine deamination is the final hydrogen transfer from a water molecule to the amine which results in the formation of ammonia. Tunneling effects lowered the activation energy by only 1–2 kJ/mol, indicating that tunneling of nuclei does not play a significant role in these processes despite the prevalence of hydrogen-transfer steps.

Copper-Catalyzed Ring-Opening/Borylation of Cyclopropenes

Copper-Catalyzed Ring-Opening/Borylation of Cyclopropenes

Reactivity of an air-stable dihydrobenzoimidazole n-dopant with organic semiconductor molecules

Summary 1,3-Dimethyl-2-(4-(dimethylamino)phenyl)-2,4-dihydro-1H-benzoimidazole, N-DMBI-H, is widely used as an air-stable n-dopant for organic semiconductors. Here, its reactivity is investigated with a variety of imide- and amide-containing semiconductor molecules that have reduction potentials in the range −0.54 to −1.10 V versus ferrocene. Reaction rates correlate poorly with these potentials. The more reactive of the imides form the corresponding radical anions cleanly, but kinetic isotope studies using N-DMBI-D indicate that the reaction proceeds via an initial hydride- or hydrogen-transfer step. For an amide- and ester-rigidified bis(styryl)benzene derivative the hydride-reduced product is stable under an inert atmosphere and can be observed directly; the radical anion can only be obtained in sub-stoichiometric yield and under certain reaction conditions. On the other hand, (N-DMBI)2 rapidly reduces all the imides and amides examined to the corresponding radical anions. The implications of these findings for dopant selection and use are discussed.

Hydrogenation of CO2 to methanol catalyzed by a manganese pincer complex: insights into the mechanism and solvent effect.

Herein, density functional theory (DFT) calculations were employed to explore the reaction mechanism of three cascade cycles for the hydrogenation of carbon dioxide to methanol (CO2 + 3H2 → CH3OH + H2O) catalyzed by a manganese pincer complex [Mn(Ph2PCH2SiMe2)2N(CO)2]. The three cascade cycles involve: the hydrogenation of CO2 to formic acid, the hydrogenation of formic acid to methanediol and the decomposition of methanediol to formaldehyde and water, and the hydrogenation of formaldehyde to methanol. The calculated results demonstrate that hydrogen activation is the rate-determining step of each catalytic cycle under solvent-free conditions, and the energy span of the whole reaction is 27.1 kcal mol-1. Furthermore, the solvent was found to be of importance in this reaction. In three different solvents, the rate-determining steps of this reaction are all the hydrogen transfer step of the formic acid hydrogenation stage, and the corresponding energy spans in water, toluene and THF solvents are 21.3, 20.8 and 20.4 kcal mol-1, respectively. Such a low energy span implies that this manganese complex could be a promising catalyst for the efficient conversion of CO2 and H2 to methanol at temperatures below 100-150 °C.

On-Surface Synthesis of a Five-Membered Carbon Ring from a Terminal Alkynyl Bromide: A [4 + 1] Annulation.

We report an on-surface synthesis of five-membered carbon ring via a [4 + 1] annulation reaction, starting from a simple terminal alkynyl bromide, 4-(bromoethynyl)biphenyl, on Ag(110). The combination of scanning tunneling microscopy (STM), synchrotron radiation photoemission spectroscopy (SRPES), and density functional theory (DFT) calculations unravel the reaction pathway and mechanism. Three basic reaction steps are involved, successively including the formation of alkynyl-Ag-alkynyl bridged organometallic dimer, the generation of alkylidene carbene intermediate, and the final [4 + 1] annulation involving a hydrogen transfer step.

A new mechanism of metal-ligand cooperative catalysis in transfer hydrogenation of ketones

We report iridium catalysts IrCl(η5-Cp⁎)(κ2-(2-pyridyl)CH2NSO2C6H4X) (1-Me, X = CH3 and 1-F, X = F) for transfer hydrogenation of ketones with 2-propanol that operate by a previously unseen metal-ligand cooperative mechanism. Under the reaction conditions, complexes 1 (1-Me and 1-F) derivatize to a series of catalytic intermediates: Ir(η5-Cp⁎)(κ2-(C5H4N)CHNSO2Ar) (2), IrH(η5-Cp⁎)(κ2-(2-pyridyl)CH2NSO2Ar) (3), and Ir(η5-Cp⁎)(κ3-(2-pyridyl)CH2NSO2Ar) (4). The structures of 1-Me and 4-Me were established by single-crystal X-ray diffraction. A rate-determining, concerted hydrogen transfer step (2 + R2CHOH ⇄ 3 + R2CO) is suggested by kinetic isotope effects, Eyring parameters (ΔH≠ = 29.1(8) kcal mol−1 and ΔS≠ = −17(19) eu), proton-hydride fidelity, and DFT calculations. According to DFT, a nine-membered cyclic transition state is stabilized by an alcohol molecule that serves as a proton shuttle.

Role of Graphitic Nitrogen and π-Conjugated Functional Groups in Selective Oxidation of Alcohols: A DFT based Mechanistic Elucidation.

Selective oxidation of alcohols to aldehydes is challenging reaction due to its accessibility to overoxidation. In this study, we have made an attempt to unravel the mechanistic aspects of selective oxidation of allyl alcohols that contain multiple functional groups catalyzed by N-doped graphene. The role of graphitic nitrogen and the presence of π-conjugated functional groups are demonstrated using the state-of-the-art density functional theory calculations. The detailed reaction mechanism for aerobic oxidation of allyl alcohol (AA) and cinnamyl alcohol (CA) are investigated. The formation of activated oxygen species (AOS) over N-doped graphene (NG) has been adopted from our previous report. The results revealed that ketonic AOS oxidizes allyl alcohols into aldehydes selectively with a relatively lower activation barrier of 20.1 kcal mol-1 . The oxidation of alcohols with the AOS formed at the edge results in high activation barriers owing to its high thermodynamic stability. Similarly, AOS formed at the center leads to the formation of H2 O2 along with high activation barriers. As a consequence, AOS formed at the center is less active when compared to ketonic AOS. The overoxidation of aldehyde is only possible due to the formation of H2 O2 . However, it is unlikely to happen due to unfavorable ambient conditions. The presence of multiple π-conjugated functional groups is responsible for the significant reduction in the activation barriers of the second hydrogen transfer step due to the stabilization of intermediate by increasing the acidic nature of the intermediates. On the basis of the results, a generalized reaction mechanism has been proposed. These results would definitely shed light on the effective fabrication of catalysts for oxidation of alcohol and sustainable energy.

Adaptive Dimensional Decoupling for Compression of Quantum Nuclear Wave Functions and Efficient Potential Energy Surface Representations through Tensor Network Decomposition.

We present an approach to reduce the computational complexity and storage pertaining to quantum nuclear wave functions and potential energy surfaces. The method utilizes tensor networks implemented through sequential singular value decompositions. Two specific forms of tensor networks are considered to adaptively compress the data in multidimensional quantum nuclear wave functions and potential energy surfaces. In one case the well-known matrix product state approximation is used whereas in another case the wave function and potential energy surface space is initially partitioned into "system" and "bath" degrees of freedom through singular value decomposition, following which the individual system and bath tensors (wave functions and potentials) are in turn decomposed as matrix product states. We postulate that this leads to a mean-field version of the well-known projectionally entangled pair state known in the tensor networks community. Both formulations appear as special cases of more general higher order singular value decompositions known in the mathematics literature as Tucker decomposition. The networks are then used to study the hydrogen transfer step in the oxidation of isoprene by peroxy and hydroxy radicals. We find that both networks are extremely efficient in accurately representing quantum nuclear eigenstates and potential energy surfaces and in computing inner products between quantum nuclear eigenstates and a final-state basis to yield product side probabilities. We also present formal protocols that will be useful to perform explicit quantum nuclear dynamics.

Efficient Solar-Driven Hydrogen Transfer by Bismuth-Based Photocatalyst with Engineered Basic Sites.

Photocatalytic organic conversions involving a hydrogen transfer (HT) step have attracted much attention, but the efficiency and selectivity under visible light irradiation still needs to be significantly enhanced. Here we have developed a noble metal-free, basic-site engineered bismuth oxybromide [Bi24O31Br10(OH)δ] that can accelerate the photocatalytic HT step in both reduction and oxidation reactions, i.e., nitrobenzene to azo/azoxybenzene, quinones to quinols, thiones to thiols, and alcohols to ketones under visible light irradiation and ambient conditions. Remarkably, quantum efficiencies of 42% and 32% for the nitrobenzene reduction can be reached under 410 and 450 nm irradiation, respectively. The Bi24O31Br10(OH)δ photocatalyst also exhibits excellent performance in up-scaling and stability under visible light and even solar irradiation, revealing economic potential for industrial applications.

Catalytic Hydrogen Transfer and Decarbonylation of Aromatic Aldehydes on Ru and Ru Phosphide Model Catalysts

Transition-metal and metal phosphide nanoparticles catalyze hydrogen-transfer steps that reduce biomass-derived aldehydes using either gaseous H2 or organic hydrogen donors (e.g., alcohols) and pro...

Selective deuteration illuminates the importance of tunneling in the unimolecular decay of Criegee intermediates to hydroxyl radical products

Ozonolysis of alkenes, an important nonphotolytic source of hydroxyl (OH) radicals in the atmosphere, proceeds through unimolecular decay of Criegee intermediates. Here, we report a large kinetic isotope effect associated with the rate-limiting hydrogen-transfer step that releases OH radicals for a prototypical Criegee intermediate, CH3CHOO. IR excitation of selectively deuterated syn-CD3CHOO is shown to result in deuterium atom transfer and release OD radical products. Vibrational activation of syn-CD3CHOO is coupled with direct time-resolved detection of OD products to measure a 10-fold slower rate of unimolecular decay upon deuteration in the vicinity of the transition state barrier, which is confirmed by microcanonical statistical theory that incorporates quantum mechanical tunneling. The corresponding kinetic isotope effect of ∼10 is attributed primarily to the decreased probability of D-atom vs. H-atom transfer arising from tunneling. Master equation modeling is utilized to compute the thermal unimolecular decay rates for selectively and fully deuterated syn methyl-substituted Criegee intermediates under atmospheric conditions. At 298 K (1 atm), tunneling is predicted to enhance the thermal decay rate of syn-CH3CHOO compared with the deuterated species, giving rise to a significant kinetic isotope effect of ∼50.