Efficient Hydrogenation of N-Heterocycles Catalyzed by NNP-Manganese(I) Pincer Complexes at Ambient Temperature.

Manganese-catalyzed hydrogenation reactions have aroused widespread interest in recent years. Among the catalytic systems described, especially PNP- and NNP-Mn pincer catalysts have been reported for the hydrogenation of aldehydes, ketones, nitriles, aldimines and esters. Furthermore, NNP-Mn pincer compounds are efficient catalysts for the hydrogenolysis of less reactive amides, ureas, carbonates, and carbamates. Herein, the synthesis and application of specific imidazolylaminophosphine ligands and the corresponding Mn pincer complexes are described. These new catalysts have been characterized and studied by a combination of experimental and theoretical investigations, and their catalytic activities have been tested in several hydrogenation reactions with good to excellent performance. Especially, the reduction of N-heterocycles can be performed under very mild conditions.

A High-Throughput Approach to Repurposing Olefin Polymerization Catalysts for Polymer Upcycling.

Efficient and economical plastic waste upcycling relies on the development of catalysts capable of polymer degradation. A systematic high-throughput screening of twenty-eight polymerization catalyst precursors, belonging to the catalyst families of metallocenes, ansa-metallocenes, and hemi- and post-metallocenes, in cis-1,4-polybutadiene (PB) degradation reveals, for the first time, important structure-activity correlations. The upcycling conditions involve activation of the catalysts (at 0.18 % catalyst loading) with tri-iso-butyl aluminum at 50 °C in toluene. The data indicate the ability to degrade PB is a general reactivity profile of neutral group 4 metal hydrides. A simple quantitative-structure activity relationship (QSAR) model utilizing two descriptors for the distribution of steric bulk in the active pocket and one measuring the metal ion electrophilicity reveals the degradation ability improves with increased but not overbearing steric congestion and lower electrophilicity.

Understanding the Deactivation Pathways of Iridium(III) Pyridine-Carboxiamide Catalysts for Formic Acid Dehydrogenation.

The degradation pathways of highly active [Cp*Ir(κ2 -N,N-R-pica)Cl] catalysts (pica=picolinamidate; 1 R=H, 2 R=Me) for formic acid (FA) dehydrogenation were investigated by NMR spectroscopy and DFT calculations. Under acidic conditions (1 equiv. of HNO3 ), 2 undergoes partial protonation of the amide moiety, inducing rapid κ2 -N,N to κ2 -N,O ligand isomerization. Consistently, DFT modeling on the simpler complex 1 showed that the κ2 -N,N key intermediate of FA dehydrogenation (INH ), bearing a N-protonated pica, can easily transform into the κ2 -N,O analogue (INH2 ; ΔG≠ ≈11 kcal mol-1 , ΔG ≈-5 kcal mol-1 ). Intramolecular hydrogen liberation from INH2 is predicted to be rather prohibitive (ΔG≠ ≈26 kcal mol-1 , ΔG≈23 kcal mol-1 ), indicating that FA dehydrogenation should involve mostly κ2 -N,N intermediates, at least at relatively high pH. Under FA dehydrogenation conditions, 2 was progressively consumed, and the vast majority of the Ir centers (58 %) were eventually found in the form of Cp*-complexes with a pyridine-amine ligand. This likely derived from hydrogenation of the pyridine-carboxiamide via a hemiaminal intermediate, which could also be detected. Clear evidence for ligand hydrogenation being the main degradation pathway also for 1 was obtained, as further confirmed by spectroscopic and catalytic tests on the independently synthesized degradation product 1 c. DFT calculations confirmed that this side reaction is kinetically and thermodynamically accessible.

How Divalent Cations Interact with the Internal Channel Site of Guanine Quadruplexes.

The front cover artwork is provided by the TheoCheM group of the Vrije Universiteit Amsterdam. The image shows that guanine quadruplexes have a stronger binding affinity for divalent cations than monovalent cations. Read the full text of the Article at 10.1002/cphc.202100529.

How Divalent Cations Interact with the Internal Channel Site of Guanine Quadruplexes.

The formation of guanine quadruplexes (GQ) in DNA is crucial in telomere homeostasis and regulation of gene expression. Pollution metals can interfere with these DNA superstructures upon coordination. In this work, we study the affinity of the internal GQ channel site towards alkaline earth metal (Mg2+ , Ca2+ , Sr2+ , and Ba2+ ), and (post-)transition metal (Zn2+ , Cd2+ , Hg2+ , and Pb2+ ) cations using density functional theory computations. We find that divalent cations generally bind to the GQ cavity with a higher affinity than conventional monovalent cations (e. g. K+ ). Importantly, we establish the nature of the cation-GQ interaction and highlight the relationship between ionic and nuclear charge, and the electrostatic and covalent interactions. The covalent interaction strength plays an important role in the cation affinity and can be traced back to the relative stabilization of cations' unoccupied atomic orbitals. Overall, our findings contribute to a deeper understanding of how pollution metals could induce genomic instability.

Reactivity Trends of Lewis Acidic Sites in Methylaluminoxane and Some of Its Modifications.

The established model cluster (AlOMe)16(AlMe3)6 for methylaluminoxane (MAO) cocatalyst has been studied by density functional theory, aiming to rationalize the different behaviors of unmodified MAO and TMA-depleted MAO/BHT (TMA = trimethylaluminum; BHT = 2,6-di-tert-butyl-4-methylphenol), highlighted in previous experimental studies. The tendency of the three model Lewis acidic sites A-C to release neutral Al fragments (i.e., AlMe2R; R = Me or bht) or transient aluminum cations (i.e., [AlMeR]+) has been investigated both in the absence and in the presence of neutral N-donors. Sites C are most likely responsible for the activation capabilities of TMA-rich MAO, but TMA depletion destabilizes them, possibly inducing structural rearrangements. The remaining sites A and B, albeit of lower Lewis acidity, should be still able to release cationic Al fragments when TMA-depleted modified MAOs are treated with N-donors (e.g. [AlMe(bht)]+ from MAO/BHT). These findings provide tentative interpretations for earlier observations of donor-dependent ionization tendencies of MAO and MAO/BHT and how TMA depleted MAOs can still be potent activators.

Secondary Electrostatic Interaction Model Revised: Prediction Comes Mainly from Measuring Charge Accumulation in Hydrogen-Bonded Monomers.

The secondary electrostatic interaction (SEI) model is often used to predict and explain relative hydrogen bond strengths of self-assembled systems. The SEI model oversimplifies the hydrogen-bonding mechanisms by viewing them as interacting point charges, but nevertheless experimental binding strengths are often in line with the model's predictions. To understand how this rudimentary model can be predictive, we computationally studied two tautomeric quadruple hydrogen-bonded systems, DDAA-AADD and DADA-ADAD. Our results reveal that when the proton donors D (which are electron-donating) and the proton acceptors A (which are electron-withdrawing) are grouped together as in DDAA, there is a larger accumulation of charge around the frontier atoms than when the proton donor and acceptor groups are alternating as in DADA. This accumulation of charge makes the proton donors more positive and the proton acceptors more negative, which enhances both the electrostatic and covalent interactions in the DDAA dimer. The SEI model is thus predictive because it provides a measure for the charge accumulation in hydrogen-bonded monomers. Our findings can be understood from simple physical organic chemistry principles and provide supramolecular chemists with meaningful understanding for tuning hydrogen bond strengths and thus for controlling the properties of self-assembled systems.

Extraction of Reliable Molecular Information from Diffusion NMR Spectroscopy: Hydrodynamic Volume or Molecular Mass?

Measuring accurate translational self-diffusion coefficients (Dt ) by NMR techniques with modern spectrometers has become rather routine. In contrast, the derivation of reliable molecular information therefrom still remains a nontrivial task. In this paper, two established approaches to estimating molecular size in terms of hydrodynamic volume (VH ) or molecular weight (M) are compared. Ad hoc designed experiments allowed the critical aspects of their application to be explored by translating relatively complex theoretical principles into practical take-home messages. For instance, comparing the Dt values of three isosteric Cp2 MCl2 complexes (Cp=cyclopentadienyl, M=Ti, Zr, Hf), having significantly different molecular mass, provided an empirical demonstration that VH is the critical molecular property affecting Dt . This central concept served to clarify the assumptions behind the derivation of Dt =ƒ(M) power laws from the Stokes-Einstein equation. Some pitfalls in establishing log (Dt ) versus log (M) linear correlations for a set of species have been highlighted by further investigations of selected examples. The effectiveness of the Stokes-Einstein equation itself in describing the aggregation or polymerization of differently shaped species has been explored by comparing, for example, a ball-shaped silsesquioxane cage with its cigar-like dimeric form, or styrene with polystyrene macromolecules.

RNA versus DNA G-Quadruplex: The Origin of Increased Stability.

DNA quadruplexes have been the subject of investigation because of their biological relevance and because of their potential application in supramolecular chemistry. Similarly, RNA quadruplexes are now gaining increasing attention. Although DNA and RNA quadruplexes are structurally very similar, the latter show higher stability. In this study we report dispersion-corrected density functional theory (DFT-D) quantum chemical calculations that were undertaken to understand the difference in stabilities of RNA and DNA quadruplexes. The smallest meaningful model of a stack of quartets, interacting with alkali metal cations, was simulated in an aqueous environment. The energy decomposition analysis allows for in-depth examination of the interaction energies, emphasising the role of noncovalent interactions and better electrostatics in determining RNA-GQs higher stabilities, particularly pinpointing the role of the extra 2'-OH groups. Furthermore, our computations present new insights on why the cation is required for self-assembly: unexpectedly the cation is not necessary to relieve the repulsion between the oxygen atoms in the central cavity, but it is needed to overcome the entropic penalty.

Impact of Conformational Effects on the Ring-Chain Equilibrium of Hydrogen-Bonded Dinucleosides.

Supramolecular ring-versus-chain equilibria are ubiquitous in biological and synthetic systems. Understanding the factors that decide whether a system will fall on one side or the other is crucial to the control of molecular self-assembly. This work reports results with two kinds of dinucleoside monomers, in which the balance between closed cycles and open polymers is found to depend on subtle factors that rule conformational equilibria, such as steric hindrance, intramolecular interactions, or π-conjugation pathways.

Reversible Self-Assembly of Water-Soluble Gold(I) Complexes.

The reaction of the gold polymers containing bipyridyl and terpyridyl units, [Au(C≡CC15H10N3)]n and [Au(C≡CC10H7N2)]n, with the water-soluble phosphines 1,3,5-triaza-7-phosphatricyclo[3.3.1.13.7]decane and 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane gives rise to the formation of four gold(I) alkynyl complexes that self-assemble in water (H2O) and dimethyl sulfoxide (DMSO), through different intermolecular interactions, with an impact on the observed luminescence displayed by the supramolecular assemblies. A detailed analysis carried out by NMR studies performed in different DMSO/deuterated H2O mixtures indicates the presence of two different assembly modes in the aggregates: (i) chain assemblies, which are based mainly on aurophilic interactions, and (ii) stacked assemblies, which are based on Au···π and π···π interactions. These different supramolecular environments can also be detected by their intrinsic optical properties (differences in absorption and emission spectra) and are predicted by the changes in the relative binding energy from density functional theory calculations carried out in DMSO and H2O. Small-angle X-ray scattering (SAXS) experiments performed in the same mixture of solvents are in agreement with the formation of aggregates in all cases. The aromatic units chosen, bipyridine and terpyridine, allow the use of external stimuli to reversibly change the aggregation state of the supramolecular assemblies. Interaction with the Zn2+ cation is observed to disassemble the aggregates, while encapsulating agents competing for Zn2+ complexation revert the process to the aggregation stage, as verified by SAXS and NMR. The adaptive nature of the supramolecular assemblies to the metal-ion content is accompanied by significant changes in the absorption and emission spectra, signaling the aggregation state and also the content on Zn2+.

Oxidation of organic diselenides and ditellurides by H2O2 for bioinspired catalyst design.

The reactivity of diselenides and ditellurides of general formula (RX)2 (X = Se, Te; R = H, CH3, Ph) toward hydrogen peroxide was studied through a computational approach based on accurate Density Functional Theory (DFT) calculations. The aliphatic and aromatic dichalcogenides have been chosen in light of their activity in glutathione peroxidase (GPx)-like catalytic cycles and their promising features as efficient antioxidant compounds. The reaction products, the energetics and the mechanistic details of these oxidations are discussed. Analogous disulfides are included in our analysis for completeness. We find that the barrier for oxidation of dichalcogenides decreases from disulfides to diselenides to ditellurides. On the other hand, variation of the substituents at the chalcogen nucleus has relatively little effect on the reactivity.

Insights on selenium and tellurium diaryldichalcogenides: A benchmark DFT study.

Selenium based diaryl dichalcogenides are compounds that are receiving attention in organic synthesis as eco-friendly oxidation agents as well as in pharmaceutical chemistry, where, together with tellurium-based derivatives, are appealing drugs mainly for their antioxidant properties. A benchmark study to establish optimal density functional theory (DFT) methods for the description of their molecular and electronic structure as well as for their energetics is presented here. Structural features, such as the orientation of the phenyl rings, as well as energetic aspects, i.e., the chalcogen-chalcogen bond strength, are discussed, with the aim of applying the novel insights to quantum mechanics-based investigations of their reactivity and to facilitate drug design. © 2016 Wiley Periodicals, Inc.

Modified Guanines as Constituents of Smart Ligands for Nucleic Acid Quadruplexes.

Repetitive guanine-rich nucleic acid sequences play a crucial role in maintaining genome stability and the cell life cycle and represent potential targets for regulatory drugs. Recently, it has been demonstrated that guanine-based ligands with a porphyrin core can be used as markers of G-quadruplex assemblies in cell tissues. Herein, model systems of guanine-based ligands are explored by DFT methods. The energies of formation of modified guanine tetrads and those of modified tetrads stacked on the top of natural guanine tetrads have been calculated. The interaction energy has been decomposed into contributions from hydrogen bonding, stacking, and ion coordination and a twist-rise potential energy scan has been performed to find the individual local minima. Energy decomposition analysis reveals the impact of various substituents (F, Cl, Br, I, Me, NMe2 ) on individual energy terms. In addition, cooperative reinforcement in forming the modified and stacked tetrads, as well as the frontier orbitals participating in the hydrogen-bonding framework involving the HOMO-LUMO gap between the occupied σHOMO on the proton-accepting C=O and =N- groups and unoccupied σLUMO on the N-H groups, has been studied. The investigated systems are demonstrated to have a potential in ligand development, mainly due to stacking enhancement compared with natural guanine, which is used as a reference.

Cocatalyst effects in Hf-catalysed olefin polymerization: taking well-defined Al-alkyl borate salts into account.

Hafnium catalysts for olefin polymerization are often very sensitive to the nature of cocatalysts, especially if they contain "free" aluminium trialkyls. Herein, cocatalyst effects in Hf-catalysed propene polymerization are examined for four Hf catalysts belonging to the family of CS-symmetric (Hf-CS-Met) and C2-symmetric (Hf-C2-Met) metallocenes, as well as of octahedral (Hf-OOOO) and pentacoordinated (Hf-PyAm) "post-metallocenes". The performance of the recently developed {[iBu2(PhNMe2)Al]2(µ-H)}+[B(C6F5)4]- (AlHAl) cocatalyst is compared with that of established systems like methylalumoxane, phenol-modified methylalumoxane and trityl borate/tri-iso-butylaluminium. The worst catalytic performance is observed with MAO. Conversely, the best cocatalyst varies depending on the Hf catalyst used and the performance indicator of interest, highlighting the complexity and importance of selecting the right precatalyst/cocatalyst combination. AlHAl proved to be a suitable system for all catalysts tested and, in some cases, it provides the best performance in terms of productivity (e.g. with hafnocenes). Furthermore, it generally leads to high molecular weight polymers, also with catalysts enabling easy chain transfer to Al like Hf-PyAm. This suggests that AlHAl has a low tendency to form heterodinuclear adducts with the cationic active species, therefore preventing the formation of dormant sites and/or termination events by chain transfer to Al.

A Hydrocarbon Soluble, Molecular and "Complete" Al-Cocatalyst for High Temperature Olefin Polymerization.

The dinuclear aluminum salt {[iBu2(DMA)Al]2(µ-H)}+[B(C6F5)4]- (AlHAl; DMA = N,N-dimethylaniline) is the prototype of a new class of molecular cocatalysts for catalytic olefin polymerization, its modular nature offering easy avenues for tailoring the activator to specific needs. We report here, as proof of concept, a first variant (s-AlHAl) bearing p-hexadecyl-N,N-dimethylaniline (DMAC16) units, which enhances solubility in aliphatic hydrocarbons. The novel s-AlHAl was used successfully as an activator/scavenger in ethylene/1-hexene copolymerization in a high-temperature solution process.

Classical Force-Field Parameters for CsPbBr3 Perovskite Nanocrystals.

Understanding the chemico-physical properties of colloidal semiconductor nanocrystals (NCs) requires exploration of the dynamic processes occurring at the NC surfaces, in particular at the ligand-NC interface. Classical molecular dynamics (MD) simulations under realistic conditions are a powerful tool to acquire this knowledge because they have good accuracy and are computationally cheap, provided that a set of force-field (FF) parameters is available. In this work, we employed a stochastic algorithm, the adaptive rate Monte Carlo method, to optimize FF parameters of cesium lead halide perovskite (CsPbBr3) NCs passivated with typical organic molecules used in the synthesis of these materials: oleates, phosphonates, sulfonates, and primary and quaternary ammonium ligands. The optimized FF parameters have been obtained against MD reference trajectories computed at the density functional theory level on small NC model systems. We validated our parameters through a comparison of a wide range of nonfitted properties to experimentally available values. With the exception of the NC-phosphonate case, the transferability of the FF model has been successfully tested on realistically sized systems (>5 nm) comprising thousands of passivating organic ligands and solvent molecules, just as those used in experiments.

The Reactivity of CsPbBr3 Nanocrystals toward Acid/Base Ligands.

The interaction of lead bromide perovskite nanocrystals with charged ligands, such as salts, zwitterions, or acid-base pairs, has been extensively documented over the past few years. On the other hand, little is known about the reactivity of perovskite nanocrystals toward neutral ligands. To fill this gap, in this work we study the interaction of CsPbBr3 nanocrystals passivated with didodecyldimethylammonium bromide (DDABr) toward a series of exogenous acid/base ligands using a combined computational and experimental approach. Our analysis indicates that DDABr-capped nanocrystals are inert toward most ligands, except for carboxylic, phosphonic, and sulfonic acids. In agreement with the calculations, our experimental results indicate that the higher the acidity of the ligands employed in the treatment, the more etching is observed. In detail, dodecylbenzenesulfonic acid (pKa = -1.8) is found to etch the nanocrystals, causing their complete degradation. On the other hand, oleic and oleylphosphonic acids (pKa 9.9 and 2, respectively) interact with surface-bound DDA molecules, causing their displacement as DDABr in various amounts, which can be as high as 40% (achieved with oleylphosphonic acid). Despite the stripping of DDA ligands, the optical properties of the nanocrystals, as well as structure and morphology, remain substantially unaffected, empirically demonstrating the defect tolerance characterizing such materials. Our study provides not only a clear overview on the interaction between perovskite nanocrystals and neutral ligands but also presents an effective ligand stripping strategy.

Halide perovskites as disposable epitaxial templates for the phase-selective synthesis of lead sulfochloride nanocrystals.

Colloidal chemistry grants access to a wealth of materials through simple and mild reactions. However, even few elements can combine in a variety of stoichiometries and structures, potentially resulting in impurities or even wrong products. Similar issues have been long addressed in organic chemistry by using reaction-directing groups, that are added to a substrate to promote a specific product and are later removed. Inspired by such approach, we demonstrate the use of CsPbCl3 perovskite nanocrystals to drive the phase-selective synthesis of two yet unexplored lead sulfochlorides: Pb3S2Cl2 and Pb4S3Cl2. When homogeneously nucleated in solution, lead sulfochlorides form Pb3S2Cl2 nanocrystals. Conversely, the presence of CsPbCl3 triggers the formation of Pb4S3Cl2/CsPbCl3 epitaxial heterostructures. The phase selectivity is guaranteed by the continuity of the cationic subnetwork across the interface, a condition not met in a hypothetical Pb3S2Cl2/CsPbCl3 heterostructure. The perovskite domain is then etched, delivering phase-pure Pb4S3Cl2 nanocrystals that could not be synthesized directly.

Hafnium vs. Zirconium, the Perpetual Battle for Supremacy in Catalytic Olefin Polymerization: A Simple Matter of Electrophilicity?

The performance of C2-symmetric ansa-hafnocene catalysts for isotactic polypropylene typically deteriorates at increasing temperature much faster than that of their zirconium analogues. Herein, we analyze in detail a set of five Hf/Zr metallocene pairs-including some of the latest generation catalysts-at medium- to high-polymerization temperature. Quantitative structure-activity relationship (QSAR) models for stereoselectivity, the ratio allyl/vinyl chain ends, and 2,1/3,1 misinsertions in the polymer indicate a strong dependence of polymerization performance on electrophilicity of the catalyst, which is a function of the ligand framework and the metal center. Based on this insight, the stronger performance decline of hafnocenes is ascribed to electrophilicity-dependent stabilization effects.