Syn-Aminoauration versus Anti-Aminoauration of Alkynes in Au(I)/Au(III) Catalysis: Understanding the Origin of Selectivity.

There is no experimental evidence of whether such gold-catalyzed aminoauration reactions follow the anti- and/or syn-pathway, and hence, to understand the origin of the selectivity in Au(I)- and Au(III)-catalyzed reactions of alkynes, a thorough mechanistic study was performed using DFT methods. The NBO and ASM analyses provided significant information about the structure-stability-reactivity of the pathway-determining states (PDS). This study further reveals that the oxidation states and geometries of gold, the steric bulk, and the dihedral angles of the PDS direct the mechanistic pathways and control the turnover frequency.

Machine Learning-Enabled Predictions of Condensed Fukui Functions and Designing of Metal Pincer Complexes for Catalytic Hydrogenation of CO2.

This research showcases the machine learning (ML)-enabled homogeneous catalyst discovery to be employed in carbon dioxide hydrogenation. To achieve the desired turnover frequency (TOF), the electrophilicity of the central metal atom is a crucial factor in transition metal pincer complexes. The condensed Fukui function is a direct measure of the catalytic performance of these pincer complexes. Herein, we demonstrate that machine learning is a convenient and effiecient method to calculate condensed Fukui functions of the central metal atom. The electrophilicity values of 202 pincer complexes were calculated by using density functional theory (DFT) to train the ML model. The test data of the experimentally established pincer complexes show a direct linkage between calculated electrophilicity and experimental TOF. Further, this data was used to develop an ML protocol to screen 2,84,062 catalyst complexes to get the electrophilicity values of the Mn, Fe, Co, and Ni transition metals encompassing various permutation combinations of PNP, PNN, NNN, and PCP pincer ligands. These findings validate the efficacy of machine learning in the rapid screening of metal pincer catalysts based on condensed Fukui functions.

Insights into the CO2 Capture Capacity of Covalent Organic Frameworks.

An inexpensive computational method is designed to demonstrate the efficacy of the complex COF toward CO2 capture. The interaction energy calculations of small repeating units of COF precisely demonstrate CO2 uptake capacity at high pressure and effective dual descriptors values of these repeating units of COFs accurately establish their structure-property relationships under ambient conditions. The computational findings are in consonance with experimental results reported by Yaghi and coworkers. Further, the computationally modelled COFs confirms that the addition of -NH2 increases the effective dual descriptors values of COFs. Whereas an increase in the size of a central aromatic unit of COF6 shows better interactions. Interaction energy and effective dual descriptor calculations demonstrate the CO2 capture abilities of COFs at high pressure and low pressure respectively. The method developed by our group would be useful in high throughput designing and screening of a large number of complex COFs at different pressure.

A Shuttle Catalysis: Elucidating a True Reaction Mechanism Involved in the Palladium Xantphos-Assisted Transposition of Aroyl Chloride and Aryl Iodide Functional Groups.

A thorough DFT study was performed to unravel the true mechanism involved in the Pd(0)-catalyzed functional group transposition between aroyl chlorides and aryl iodides. Two different experimental groups proposed different mechanisms for the functional group transposition reaction. A careful assessment of experimental findings and thorough computational studies endorsed that the functional group transposition proceeds via phosphonium salt formation and ligand-enabled C-P bond metathesis, leading to the formation of the PhI and the intermediate 2. After the formation of the intermediate 2, the transposition of functional groups takes place through the interpalladium ligand exchange mechanism, where two palladium centers act as shuttle catalysts. In short, both C-P bond metathesis and interpalladium ligand exchange steps are crucial in the functional group transposition mechanism.

Ascendancy of Nitrogen Heterocycles in the Computationally Designed Mn(I)PNN Pincer Catalysts on the Hydrogenation of Carbon Dioxide to Methanol.

The development of sustainable catalysts to get methanol from CO2 under milder conditions and without any additives is still considered an arduous task. In many instances, transition-metal-catalyzed carbon dioxide to formic acid formation is more facile than methanol formation. This article provides comprehensive density functional theoretic investigations of six new Mn(I)PNN complexes, which are designed to perform CO2 to methanol conversion under milder reaction conditions. All these six catalysts have similar structural features except at terminal nitrogen, -N (1), where adenine-inspired nitrogen heterocycles containing pyridine and pyrimidine moieties are attached to instill an electron withdrawing effect on the central metal and thus to facilitate dihydrogen polarization during the catalyst regeneration. All these computationally modeled Mn(I)PNN complexes demonstrate the promising catalytic activity to get methanol through cascade catalytic cycles at 298.15 K. The metal-ligand cooperative (MLC) as well as noncooperative (NC) pathways are investigated for each catalytic cycle. The NC pathway is the preferred pathway for formic acid and formaldehyde formation, whereas methanol formation proceeds through only the MLC pathway. Different nitrogen heterocycles attached to the -N (1) terminal manifested a considerable amount of impact on the Gibbs free energies, overall activation energies, and computed turnover frequencies (TOFs). Among all the catalysts, SPCAT02 provides excellent TOFs for HCO2H (500 151 h-1), HCHO (11 912 h-1), and CH3OH (2 372 400 h-1) formation at 50 °C. SPCAT04 is found to be a better catalyst for the selective formation of formic acid formation at room temperature than the rest of the catalysts. The computed TOF results are found reliable upon comparison with experimentally established catalysts. To establish the structure-activity relationship, the activation strain model and Fukui function calculations are performed on all the catalysts. Both these studies provide complementary results. The present study revealed a very important finding that a more electrophilic metal center could facilitate the CO2 hydrogenation reaction robustly. All computationally designed catalysts could be cheaper and better alternatives to convert CO2 to methanol under mild reaction conditions in an aqueous medium.

Unraveling the Effect of Aromatic Groups in Mn(I)NNN Pincer Complexes on Carbon Dioxide Activation Using Density Functional Study.

Carbon dioxide utilization is necessary to reduce carbon footprint and also to synthesize value-added chemicals. The transition metal pincer complexes are attractive catalysts for the hydrogenation of carbon dioxide to formic acid. There is a need to understand the factors affecting the catalytic performance of these pincer complexes through a structure-activity relationship study using computational methods. It is a well-established fact that aromatic functionalities offer stability and selectivity to transition metal catalysts. However, their impact on the performance of the catalysts is lesser known in the case of metal pincer complexes. Hence, it is necessary to investigate the catalytic performance of Mn(I)NNN pincer complexes with variably activated aromatic functionalities. In this context, 15 catalysts are designed by placing different types of aromatic rings at the pincer carbons and two terminal nitrogen of Mn(I)NNN pincer complexes. A benzene moiety, placed at C2-C3 carbons of Mn(I)NNN pincer complex with identical aromatic groups at the terminal nitrogen, is found to be most efficient toward CO2 hydrogenation than the rest of the catalysts. On the other hand, when N,N-dimethyl aniline is placed at C2-C3 carbons of Mn(I)NNN pincer complexes, then the catalytic performance is significantly decreased. Thus, the present study unravels the impact of aromatic groups in Mn(I)NNN pincer complexes toward the catalytic hydrogenation of carbon dioxide.

Computational Approach to Unravel the Role of Hydrogen Bonding in the Interaction of NAMI-A with DNA Nucleobases and Nucleotides.

Density functional theory method in combination with a continuum solvation model is used to understand the role of hydrogen bonding in the interactions of tertiary nitrogen centers of guanine and adenine with monoaqua and diaqua NAMI-A. In the case of adenine, the interaction of N3 with monoaqua NAMI-A is preferred over that of N7 and N1 whereas, N7 site is the most preferred site over N3 and N1 in the diaqua ruthenium-adenine interaction. In the monoaqua and diaqua NAMI-A-guanine interactions, the N7 site is the most preferred site over the N3 site. Here, the strength and number of H-bonds play important roles in stabilizing intermediates and transition states involved in the interaction of NAMI-A and purine bases. Atoms in molecules and Becke surface analysis confirm that the interactions between monoaqua and diaqua NAMI-A with the base pairs of GC and AT dinucleotides leads to the structural deformation in the geometry of the base pairs of dinucleotides. The diaqua NAMI-A adducts induce more disruption in the base pairs as compared to monoaqua NAMI-A adducts. which suggests that diaqua NAMI-A could be a better anticancer agent than monoaqua NAMI-A. This study can be extended to envisage the potential applications of computational studies in the development of new drugs and targeted drug delivery systems.

Fenton's Reagent Catalyzed Release of Carbon Monooxide from 1,3-Dihydroxy Acetone.

Triose sugar, 1,3-dihydroxy acetone (DHA) on treatment with Fenton's reagent releases CO under physiological conditions. The release of CO has been demonstrated by myoglobin assay and quantum chemical studies. The mechanistic study has been carried out using B3LYP/6-311++G(d,p), M06-2X/6-311++G(d,p) and CCSD(T)//M06-2X/6-311++G(d,p) level of theories in aqueous medium with dielectric constant of 78.39 by employing the polarized continuum model (PCM). The theoretical investigation shows that DHA breaks down completely into 2 equiv of CO, 1 equiv of CO2, and 6 equiv of H2O without formation of toxic metabolites. The activation barriers of some steps are as high as ∼50 kcal mol-1 along with barrierless intermediate steps resulting from highly stabilized intermediates. The quantum tunneling mechanism of proton transfer steps has been confirmed through kinetic isotope effect study. The natural bond orbital analysis is consistent with the proposed mechanism. The present protocol does not require any photoactivation and thus it can serve as a promising alternative to transition metal CO-releasing molecules. The present work can initiate the study of carbohydrates as CO-releasing molecules for therapeutic applications and it could also be useful in generation of CO for laboratory applications.