Role of Anation on the Mechanism of Proton Reduction Involving a Pentapyridine Cobalt Complex: A Theoretical Study

Kinetic and thermodynamic aspects of proton reduction involving pentapyridine cobalt­(II) complex were investigated with the help of quantum chemical calculations. Free energy profile of all possible mechanistic routes for proton reduction was constructed with the consideration of both anation and solvent bound pathways. The computed free energy profile shows that acetate ion plays a significant role in modulating the kinetic aspects of Co­(III)–hydride formation which is found to be the key intermediate for proton reduction. Upon replacing solvent by acetate ion, one electron reduction and protonation of Co^I species become more rapid along with slow displacement reaction. Most favorable pathways for hydrogen evolution from Co­(III)–hydride species is also investigated. Among the four possible pathways, reduction followed by protonation of Co­(III)–hydride (RPP) is found to be the most feasible pathway. On the basis of QTAIM and NBO analyses, the electronic origin of most favorable pathway is explained. The basicity of cobalt center along with thermodynamic stability of putative Co^III/II–H species is essentially a prime factor in deciding the most favorable pathway for hydrogen evolution. Our computed results are in good agreement with experimental observations and also provided adequate information to design cobalt-based molecular electrocatalysts for proton reduction in future

Unraveling the reaction mechanism, enantio and diastereoselectivities of selenium ylide promoted epoxidation

1001-1009The reaction between chiral selenium ylide and benzaldehyde leads to the formation of (2S,3S)-trans-epoxide with high enantio- and diastereoselectivity. Density functional theory and Hartree-Fock calculations using 6-31G(d) basis set have been performed to understand the reaction mechanism and factors associated with enantio- and diastereoselectivities. Conformation of chiral selenium ylide has been found to have a strong influence on the stability of the initial addition transition state between ylide and benzaldehyde. Calculated enantio- and diastereoselectivities from the energy differences between B3LYP/6-31G(d) addition TSs are in good agreement with the experimental data. The rate and diastereoselectivity are controlled by the <i style="mso-bidi-font-style: normal">cisoid-transoid rotational transition state. Analysis of transition state geometries clearly reveals that unfavorable eclipsing interaction between phenyl groups of the benzaldehyde and ylidic substituents mainly governs the energy differences between the enantio and diastereomeric transition states. The favourable reactivity is also explained through Fukui function calculations

Structure and Reactivity of Pd Complexes in Various Oxidation States in Identical Ligand Environments with Reference to C–C and C–Cl Coupling Reactions: Insights from Density Functional Theory

Bonding and reactivity of [(^RN4)­Pd^<i>n</i>CH₃X]^{(<i>n</i>−2)+} complexes have been investigated at the M06/BS2//B3LYP/BS1 level. Feasible mechanisms for the unselective formation of ethane and methyl chloride from mono-methyl Pd^III complexes and selective formation of ethane or methyl chloride from Pd^IV complexes are reported here. Density functional theory (DFT) results indicate that Pd^IV is more reactive than Pd^III and Pd in different oxidation states that follow different mechanisms. Pd^III complexes react in three steps: (i) conformational change, (ii) transmetalation, and (iii) reductive elimination. In the first step a five-coordinate Pd^III intermediate is formed by the cleavage of one Pd–N_ax bond, and in the second step one methyl group is transferred from the Pd^III complex to the above intermediate via transmetalation, and subsequently a six-coordinate Pd^IV intermediate is formed by disproportion. In this step, transmetalation can occur on both singlet and triplet surfaces, and the singlet surface is lying lower. Transmetalation can also occur between the above intermediate and [(^RN4)­Pd^II(CH₃)­(CH₃CN) ]⁺, but this not a feasible path. In the third step this Pd^IV intermediate undergoes reductive elimination of ethane and methyl chloride unselectively, and there are three possible routes for this step. Here axial–equatorial elimination is more facile than equatorial–equatorial elimination. Pd^IV complexes react in two steps, a conformational change followed by reductive elimination, selectively forming ethane or methyl chloride. Thus, Pd^III complex reacts through a six-coordinate Pd^IV intermediate that has competing C–C and C–Cl bond formation, and Pd^IV complex reacts through a five-coordinate Pd^IV intermediate that has selective C–C and C–Cl bond formation. Free energy barriers indicate that iPr, in comparison to the methyl substituent in the ^RN4 ligand, activates the cleaving of the Pd–N_ax bond through electronic and steric interactions. Overall, reductive elimination leading to C–C bond formation is easier than the formation of a C–Cl bond

Quantum mechanical study on complexation phenomenon of pillar[5]arene towards neutral dicyanobutane

Based on density functional theory calculations, we have addressed the electronic structure, binding and nature of non-covalent interactions between alkylated pillar[5]arene (P[5]A) and 1,4-dicyanobutane (DCB)-based host-guest macrocycles. Neutral 1,4-dicyanobutane-based alkylated DCB_ProP[5]A is found to show higher binding energy when compared to the other three host-guest macrocycles. These complexes are largely stabilised by non-covalent interactions, which are ascertained through NCI and QTAIM analyses. Furthermore, the second-order perturbation energy of NBO analysis show that LP (N) – σ*(C-H) interactions predominate in DCB_ProP[5]A complex. Particularly, alkyl substituents (-methyl, -ethyl and -propyl) are playing a vital role in stabilising the host-guest complexes. In summary, the present work not only exhibits an efficient strategy to build a new family of alkylated P[5]A inclusion complexes but also providing deeper understanding on various non-covalent interactions towards 1,4-dicyanobutane (DCB) guest molecules inside the host environment.</p

Halogen-Based 17β-HSD1 Inhibitors: Insights from DFT, Docking, and Molecular Dynamics Simulation Studies

The high expression of 17β-hydroxysteroid dehydrogenase type 1 (17β-HSD1) mRNA has been found in breast cancer tissues and endometriosis. The current research focuses on preparing a range of organic molecules as 17β-HSD1 inhibitors. Among them, the derivatives of hydroxyphenyl naphthol steroidomimetics are reported as one of the potential groups of inhibitors for treating estrogen-dependent disorders. Looking at the recent trends in drug design, many halogen-based drugs have been approved by the FDA in the last few years. Here, we propose sixteen potential hydroxyphenyl naphthol steroidomimetics-based inhibitors through halogen substitution. Our Frontier Molecular Orbitals (FMO) analysis reveals that the halogen atom significantly lowers the Lowest Unoccupied Molecular Orbital (LUMO) level, and iodine shows an excellent capability to reduce the LUMO in particular. Tri-halogen substitution shows more chemical reactivity via a reduced HOMO–LUMO gap. Furthermore, the computed DFT descriptors highlight the structure–property relationship towards their binding ability to the 17β-HSD1 protein. We analyze the nature of different noncovalent interactions between these molecules and the 17β-HSD1 using molecular docking analysis. The halogen-derived molecules showed binding energy ranging from −10.26 to −11.94 kcal/mol. Furthermore, the molecular dynamics (MD) simulations show that the newly proposed compounds provide good stability with 17β-HSD1. The information obtained from this investigation will advance our knowledge of the 17β-HSD1 inhibitors and offer clues to developing new 17β-HSD1 inhibitors for future applications

Pyrene Schiff Base: Photophysics, Aggregation Induced Emission, and Antimicrobial Properties

Pyrene containing Schiff base molecule, namely 4-[(pyren-1-ylmethylene)­amino]­phenol (KB-1), was successfully synthesized and well characterized by using ¹H, ¹³C NMR, FT-IR, and EI-MS spectrometry. UV–visible absorption, steady-state fluorescence, time-resolved fluorescence, and transient absorption spectroscopic techniques have been employed to elucidate the photophysical processes of KB-1. It has been demonstrated that the absorption characteristics of KB-1 have been bathochromatically tuned to the visible region by extending the π-conjugation. The extended π-conjugation is evidently confirmed by DFT calculations and reveals that π→π* transition is the major factor responsible for electronic absorption of KB-1. The photophysical property of KB-1 was carefully examined in different organic solvents at different concentrations and the results show that the fluorescence of this molecule is completely quenched due to photoinduced electron transfer. Intriguingly, the fluorescence intensity of KB-1 increases enormously by the gradual addition of water up to 90% with concomitant increase in fluorescence lifetime. This clearly signifies that this molecule has aggregation-induced emission (AIE) property. The mechanism of AIE of this molecule is suppression of photoinduced electron transfer (PET) due to hydrogen bonding interaction of imine donor with water. A direct evidence of PET process has been presented by using nanosecond transient absorption measurements. Further, KB-1 was successfully used for antimicrobial and bioimaging studies. The antimicrobial studies were carried out through disc diffusion method. KB-1 is used against both Gram-positive (<i>Rhodococcus rhodochrous</i> and <i>Staphylococcus aureus</i>) and Gram-negative (<i>Escherichia coli</i> and <i>Pseudomonas aeruginosa</i>) bacterial species and also fungal species (<i>Candida albicans</i>). The result shows KB-1 can act as an excellent antimicrobial agent and as a photolabeling agent. <i>S. aureus</i>, <i>P. aeruginosa</i>, and <i>C. albicans</i> were found to be the most susceptible microorganisms at 1 mM concentration among the bacteria used in the present investigation