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 16 years, 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.

Heterogeneous Electrocatalytic Oxygen Evolution Reaction by a Sol-Gel Electrode with Entrapped Na3 [Ru2 (µ-CO3 )4 ]: The Effect of NaHCO3.

The Na3 [Ru2 (µ-CO3 )4 ] complex is acting as a water oxidation catalyst in a homogeneous system. Due to the significance of heterogeneous systems and the effect of bicarbonate on the kinetic, we studied the bicarbonate effect on the heterogeneous electrocatalyst by entrapping the Na3 [Ru2 (µ-CO3 )4 ] complex in a sol-gel matrix. We have developed two types of sol-gel electrodes, which differ by the precursor, and are demonstrating their stability over a minimum of 200 electrochemical cycles. The pH increases affected the currents and kcat for both types of electrodes, and their hydrophobicity, which was obtained from the precursor type, influenced the electrocatalytic process rate. The results indicate that NaHCO3 has an important role in the catalytic activity of the presented heterogeneous systems; without NaHCO3 , the diffusing species is probably OH- , which undergoes diffusion via the Grotthuss mechanism. To the best of our knowledge, this is the first study to present a simple and fast one-step entrapment process for the Na3 [Ru2 (µ-CO3 )4 ] complex by the sol-gel method under standard laboratory conditions. The results contribute to optimizing the WSP, ultimately helping expand the usage of hydrogen as a green and more readily available energy source.

Quantitative Structure-Toxicity Relationship in Bioactive Molecules from a Conceptual DFT Perspective.

The preclinical drug discovery stage often requires a large amount of costly and time-consuming experiments using huge sets of chemical compounds. In the last few decades, this process has undergone significant improvements by the introduction of quantitative structure-activity relationship (QSAR) modelling that uses a certain percentage of experimental data to predict the biological activity/property of compounds with similar structural skeleton and/or containing a particular functional group(s). The use of machine learning tools along with it has made life even easier for pharmaceutical researchers. Here, we discuss the toxicity of certain sets of bioactive compounds towards Pimephales promelas and Tetrahymena pyriformis in terms of the global conceptual density functional theory (CDFT)-based descriptor, electrophilicity index (ω). We have compared the results with those obtained by using the commonly used hydrophobicity parameter, logP (where P is the n-octanol/water partition coefficient), considering the greater ease of computing the ω descriptor. The Human African trypanosomiasis (HAT) curing activity of 32 pyridyl benzamide derivatives is also studied against Tryphanosoma brucei. In this review article, we summarize these multiple linear regression (MLR)-based QSAR studies in terms of electrophilicity (ω, ω2) and hydrophobicity (logP, (logP)2) parameters.

Enhancing the catalytic OER performance of MoS2via Fe and Co doping.

Enhancing the sluggish kinetics of the electrochemical oxygen evolution reaction (OER) is crucial for many clean-energy production technologies. Although much progress has been made in recent years, developing active, stable, and cost-effective OER electrocatalysts is still challenging. The layered MoS2, based on Earth-abundant elements, is widely explored as a promising hydrogen evolution electrocatalyst but exhibits poor OER activity. Here, we report a facile strategy to improve the sluggish OER of MoS2 through co-doping MoS2 nanosheets with Fe and Co atoms. The synergistic effect obtained by adjusting the Co/Fe ratio in the Fe-Co doped MoS2 induces electronic and structural modifications and a richer active surface area morphology resulting in a relatively low OER overpotential of 380 mV (at 10 mA cm-2). The electronic modulation upon doping was further supported by DFT calculations that show favorable interaction with the OER intermediate species, thus reducing the energy barrier for the OER. This work paves the way for future strategies for tailoring the electronic properties of transition-metal dichalcogenides (TMDCs) to activate the structure for the sluggish OER with the assistance of non-noble-metal materials.

CB6Al0/+: Planar hexacoordinate boron (phB) in the global minimum structure.

Herein, we report for the first time the presence of a planar hexacoordinate boron (phB) atom in the global minimum energy structure of a neutral cluster system. The potential energy surface (PES) has been explored for CB6Al0/+/- systems using density functional theory (DFT). The global minima of CB6Al (1a) and CB6Al+ (1b) contain a phB center. However, the global minimum of CB6Al- (1c) does not have a phB atom. The CCSD(T)/aug-cc-pVTZ level of theory has been applied to compute the relative energies of the low-lying isomers with respect to the 1a and 1b structures of CB6Al and CB6Al+ systems, respectively. The exploration of the PES of CB60/+/- systems indicates that the global minima do not contain a phB atom. However, the incorporation of an aluminium (Al) atom into the CB6 moiety produces structures containing a phB center in the CB6Al0/+ systems. Hence, the Al metal has an important role in attaining a planar geometry having a hexacoordinate boron center. The dynamical stability of CB6Al (1a) and CB6Al+ (1b) was confirmed from the atom-centered density matrix propagation (ADMP) simulation over 20 ps of time at temperatures of 300 K and 400 K. The natural charge computations showed that the charges on the phB are almost zero in both systems. The 1a structure has σ/π-dual aromaticity as predicted from the nucleus independent chemical shift (NICS) values and the gauge-including magnetically induced ring current (GIMIC).

The Role of Carbonate in Catalytic Oxidations.

CO2, HCO3-, and CO32- are present in all aqueous media at pH > 4 if no major effort is made to remove them. Usually the presence of CO2/HCO3-/CO32- is either forgotten or considered only as a buffer or proton transfer catalyst. Results obtained in the last decades point out that carbonates are key participants in a variety of oxidation processes. This was first attributed to the formation of carbonate anion radicals via the reaction OH• + CO32- → CO3•- + OH-. However, recent studies point out that the involvement of carbonates in oxidation processes is more fundamental. Thus, the presence of HCO3-/CO32- changes the mechanisms of Fenton and Fenton-like reactions to yield CO3•- directly even at very low HCO3-/CO32- concentrations. CO3•- is a considerably weaker oxidizing agent than the hydroxyl radical and therefore a considerably more selective oxidizing agent. This requires reconsideration of the sources of oxidative stress in biological systems and might explain the selective damage induced during oxidative stress. The lower oxidation potential of CO3•- probably also explains why not all pollutants are eliminated in many advanced oxidation technologies and requires rethinking of the optimal choice of the technologies applied. The role of percarbonate in Fenton-like processes and in advanced oxidation processes is discussed and has to be re-evaluated. Carbonate as a ligand stabilizes transition metal complexes in uncommon high oxidation states. These high-valent complexes are intermediates in electrochemical water oxidation processes that are of importance in the development of new water splitting technologies. HCO3- and CO32- are also very good hole scavengers in photochemical processes of semiconductors and may thus become key participants in the development of new processes for solar energy conversion. In this Account, an attempt to correlate these observations with the properties of carbonates is made. Clearly, further studies are essential to fully uncover the potential of HCO3-/CO32- in desired oxidation processes.