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An electrochemical study of frustrated Lewis pairs: a metal-free route to hydrogen oxidation.

ABSTRACT: Frustrated Lewis pairs have found many applications in the heterolytic activation of H2 and subsequent hydrogenation of small molecules through delivery of the resulting proton and hydride equivalents. Herein, we describe how H2 can be preactivated using classical frustrated Lewis pair chemistry and combined with in situ nonaqueous electrochemical oxidation of the resulting borohydride. Our approach allows hydrogen to be cleanly converted into two protons and two electrons in situ, and reduces the potential (the required energetic driving force) for nonaqueous H2 oxidation by 610 mV (117.7 kJ mol(-1)). This significant energy reduction opens routes to the development of nonaqueous hydrogen energy technology.

SUBMITTER: Lawrence EJ

PROVIDER: S-EPMC4148919 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Metal-free electrocatalytic hydrogen oxidation using frustrated Lewis pairs and carbon-based Lewis acids.

Project description:Whilst hydrogen is a potentially clean fuel for energy storage and utilisation technologies, its conversion to electricity comes at a high energetic cost. This demands the use of rare and expensive precious metal electrocatalysts. Electrochemical-frustrated Lewis pairs offer a metal-free, CO tolerant pathway to the electrocatalysis of hydrogen oxidation. They function by combining the hydrogen-activating ability of frustrated Lewis pairs (FLPs) with electrochemical oxidation of the resultant hydride. Here we present an electrochemical-FLP approach that utilises two different Lewis acids - a carbon-based N-methylacridinium cation that possesses excellent electrochemical attributes, and a borane that exhibits fast hydrogen cleavage kinetics and functions as a "hydride shuttle". This synergistic interaction provides a system that is electrocatalytic with respect to the carbon-based Lewis acid, decreases the required potential for hydrogen oxidation by 1 V, and can be recycled multiple times.

| S-EPMC5477046 | biostudies-literature

Metal-free dihydrogen oxidation by a borenium cation: a combined electrochemical/frustrated Lewis pair approach.

Project description:In order to use H2 as a clean source of electricity, prohibitively rare and expensive precious metal electrocatalysts, such as Pt, are often used to overcome the large oxidative voltage required to convert H2 into 2?H(+) and 2?e(-). Herein, we report a metal-free approach to catalyze the oxidation of H2 by combining the ability of frustrated Lewis pairs (FLPs) to heterolytically cleave H2 with the in?situ electrochemical oxidation of the resulting borohydride. The use of the NHC-stabilized borenium cation [(IiPr2)(BC8H14)](+) (IiPr2=C3H2(NiPr)2, NHC=N-heterocyclic carbene) as the Lewis acidic component of the FLP is shown to decrease the voltage required for H2 oxidation by 910?mV at inexpensive carbon electrodes, a significant energy saving equivalent to 175.6?kJ?mol(-1). The NHC-borenium Lewis acid also offers improved catalyst recyclability and chemical stability compared to B(C6F5)3, the paradigm Lewis acid originally used to pioneer our combined electrochemical/frustrated Lewis pair approach.

| S-EPMC4257500 | biostudies-literature

Parallels between Metal-Ligand Cooperativity and Frustrated Lewis Pairs.

Project description:Metal ligand cooperativity (MLC) and frustrated Lewis pair (FLP) chemistry both feature the cooperative action of a Lewis acidic and a Lewis basic site on a substrate. A lot of work has been carried out in the field of FLPs to prevent Lewis adduct formation, which often reduces the FLP reactivity. Parallels are drawn between the two systems by looking at their reactivity with CO2, and we explore the role of steric bulk in preventing dimer formation in MLC systems.

| S-EPMC6687039 | biostudies-literature

Hydrogen Activation by Frustrated and Not So Frustrated Lewis Pairs Based on Pyramidal Lewis Acid 9-Boratriptycene: A Computational Study.

Project description:Structural features and reactivity of frustrated Lewis pairs (FLPs) formed by pyramidal group 13 Lewis acids based on 9-bora and 9-alatriptycene and bulky phosphines P t Bu3, PPh3, and PCy3 are considered at the M06-2X/def2-TZVP level of theory. Classic FLP is formed only in the B(C6Me4)3CH/P t Bu3 system, while both FLP and donor-acceptor (DA) complex are observed in the B(C6F4)3CF/P t Bu3 system. Formation of DA complexes was observed in other systems; the B(C6H4)3CH·P t Bu3 complex features an elongated DA bond and can be considered a "latent" FLP. Transition states and reaction pathways for molecular hydrogen activation have been obtained. Processes of heterolytic hydrogen splitting are energetically more favored in solution compared to the gas phase, while activation energies in the gas phase and in solution are close. The alternative processes of hydrogenation of B-C or Al-C bonds in the source pyramidal Lewis acids in the absence of a Lewis base are exergonic but have larger activation energies than those for heterolytic hydrogen splitting. The tuning of Lewis acidity of 9-boratriptycene by changing the substituents allows one to control its reactivity with respect to hydrogen activation. Interestingly, the most promising system from the practical point of view is the DA complex B(C6H4)3CH·P t Bu3, which is predicted to provide both low activation energy and thermodynamic reversibility of the heterolytic hydrogen splitting process. It appears that such "not so frustrated" or "latent" FLPs are the best candidates for reversible heterolytic hydrogen splitting.

| S-EPMC9798527 | biostudies-literature

Metal-ligand multiple bonds as frustrated Lewis pairs for C-H functionalization.

Project description:The concept of frustrated Lewis pairs (FLPs) has received considerable attention of late, and numerous reports have demonstrated the power of non- or weakly interacting Lewis acid-base pairs for the cooperative activation of small molecules. Although most studies have focused on the use of organic or main-group FLPs that utilize steric encumbrance to prevent adduct formation, a related strategy can be envisioned for both organic and inorganic complexes, in which "electronic frustration" engenders reactivity consistent with both nucleophilic (basic) and electrophilic (acidic) character. Here we propose that such a description is consistent with the behavior of many coordinatively unsaturated transition-metal species featuring metal-ligand multiple bonds, and we further demonstrate that the resultant reactivity may be a powerful tool for the functionalization of C-H and E-H bonds.

| S-EPMC3510986 | biostudies-literature

Heterolytic Splitting of Molecular Hydrogen by Frustrated and Classical Lewis Pairs: A Unified Reactivity Concept.

Project description:Using a set of state-of-the-art quantum chemical techniques we scrutinized the characteristically different reactivity of frustrated and classical Lewis pairs towards molecular hydrogen. The mechanisms and reaction profiles computed for the H2 splitting reaction of various Lewis pairs are in good agreement with the experimentally observed feasibility of H2 activation. More importantly, the analysis of activation parameters unambiguously revealed the existence of two reaction pathways through a low-energy and a high-energy transition state. An exhaustive scrutiny of these transition states, including their stability, geometry and electronic structure, reflects that the electronic rearrangement in low-energy transition states is fundamentally different from that of high-energy transition states. Our findings reveal that the widespread consensus mechanism of H2 splitting characterizes activation processes corresponding to high-energy transition states and, accordingly, is not operative for H2-activating systems. One of the criteria of H2-activation, actually, is the availability of a low-energy transition state that represents a different H2 splitting mechanism, in which the electrostatic field generated in the cavity of Lewis pair plays a critical role: to induce a strong polarization of H2 that facilities an efficient end-on acid-H2 interaction and to stabilize the charge separated "H+-H-" moiety in the transition state.

| S-EPMC5700139 | biostudies-literature

Reactions of Diethylazo-Dicarboxylate with Frustrated Lewis Pairs.

Project description:Reactions of PAr3 /B(C6 F5 )3 (Ar=o-Tol, Mes, Ph) FLPs with diethyl azodicarboxylate (DEAD) afford the corresponding FLP addition products 1-3 in which P-N and B-O linkages are formed. In contrast, the reaction of BPh3 , PPh3 and DEAD gave product 4 where P-N and N-B linkages were confirmed. In all cases, other binding modes were computed to be both higher in energy and readily distinguishable by 31 P and 11 B NMR parameters. These data illustrate the influence of steric demands and electronic structures on the nature of the products of FLP reactions with DEAD.

| S-EPMC9796924 | biostudies-literature

On the hydrogen activation by frustrated Lewis pairs in the solid state: benchmark studies and theoretical insights.

Project description:Recently, the concept of small molecule activation by frustrated Lewis pairs (FLPs) has been expanded to the solid state showing a variety of interesting reactivities. Therefore, there is a need to establish a computational protocol to investigate such systems theoretically. In the present study, we selected several FLPs and applied multiple levels of theory, ranging from a semi-empirical tight-binding Hamiltonian to dispersion corrected hybrid density functionals. Their performance is benchmarked for the computation of crystal geometries, thermostatistical contributions, and reaction energies. We show that the computationally efficient HF-3c method gives accurate crystal structures and is numerically stable and sufficiently fast for routine applications. This method also gives reliable values for the thermostatistical contributions to Gibbs free energies. The meta-generalized gradient approximated TPSS-D3 evaluated in a projector augmented plane wave basis set is able to produce sufficiently accurate reaction electronic energies. The established protocol is intended to support experimental studies and to predict new reactions in the emerging field of solid-state FLPs.This article is part of the themed issue 'Frustrated Lewis pair chemistry'.

| S-EPMC5540839 | biostudies-literature

A combined "electrochemical-frustrated lewis pair" approach to hydrogen activation: surface catalytic effects at platinum electrodes.

Project description:Herein, we extend our "combined electrochemical-frustrated Lewis pair" approach to include Pt electrode surfaces for the first time. We found that the voltammetric response of an electrochemical-frustrated Lewis pair (FLP) system involving the B(C6 F5 )3 /[HB(C6 F5 )3 ](-) redox couple exhibits a strong surface electrocatalytic effect at Pt electrodes. Using a combination of kinetic competition studies in the presence of a H atom scavenger, 6-bromohexene, and by changing the steric bulk of the Lewis acid borane catalyst from B(C6 F5 )3 to B(C6 Cl5 )3 , the mechanism of electrochemical-FLP reactions on Pt surfaces was shown to be dominated by hydrogen-atom transfer (HAT) between Pt, [PtH] adatoms and transient [HB(C6 F5 )3 ](⋅) electrooxidation intermediates. These findings provide further insight into this new area of combining electrochemical and FLP reactions, and proffers additional avenues for exploration beyond energy generation, such as in electrosynthesis.

| S-EPMC4316182 | biostudies-literature

Theoretical Characterization of New Frustrated Lewis Pairs for Responsive Materials.

Project description:In recent years, responsive materials including dynamic bonds have been widely acclaimed due to their expectation to pilot advanced materials. Within these materials, synthetic polymers have shown to be good candidates. Recently, the so-called frustrated Lewis pairs (FLP) have been used to create responsive materials. Concretely, the activation of diethyl azodicarboxylate (DEAD) by a triphenylborane (TPB) and triphenylphosphine (TPP) based FLP has been recently exploited for the production of dynamic cross-links. In this work, we computationally explore the underlying dynamic chemistry in these materials, in order to understand the nature and reversibility of the interaction between the FLP and DEAD. With this goal in mind, we first characterize the acidity and basicity of several TPB and TPP derivatives using different substituents, such as electron-donating and electron-withdrawing groups. Our results show that strong electron-donating groups increase the acidity of TPB and decrease the basicity of TPP. However, the FLP-DEAD interaction is not mainly dominated by the influence of these substituents in the acidity or basicity of the TPB or TPP systems, but by attractive or repulsive forces between substituents such as hydrogen bonds or steric effects. Based on these results, a new material is proposed based on FLP-DEAD complexes.

| S-EPMC8155995 | biostudies-literature

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