Experimental Evidences on Magnetism-Covalent Bonding Interplay in Structural Properties of Solids and during Chemisorption.

Valence electrons are one of the main players in solid catalysts and in catalytic reactions, since they are involved in several correlated phenomena like chemical bonding, magnetism, chemisorption, and bond activation. This is particularly true in the case of solid catalysts containing d-transition metals, which exhibit a wide range of magnetic phenomena, from paramagnetism to collective behaviour. Indeed, the electrons of the outer d-shells are, on one hand, involved in the formation of bonds within the structure of a catalyst and on its surface, and, on the other, they are accountable for the magnetic properties of the material. For this reason, the relationship between magnetism and heterogeneous catalysis has been a source of great interest since the mid-20th century. The subject has gained a lot of attention in the last decade, thanks to the orbital engineering of quantum spin-exchange interactions and to the widespread application of external magnetic fields as boosting tools in several catalytic reactions. The topic is discussed here through experimental examples and evidences of the interplay between magnetism and covalent bonding in the structure of solids and during the chemisorption process. Covalent bonding is discussed since it represents one of the strongest contributions to bonds encountered in materials.

Structure-based Design of Novel Hepatitis B Virus Capsid Assembly Modulators.

Small-molecule capsid assembly modulators (CAMs) have been recently recognized as promising antiviral agents for curing chronic hepatitis B virus (HBV) infection. A target-based in silico screening study is described, aimed towards the discovery of novel HBV CAMs. Initial optimization of four weakly active screening hits was performed via focused library synthesis. Lead compound 42 and close analogues 56 and 57 exhibited in vitro potency in the sub- and micromolar range along with good physico-chemical properties and were further evaluated in molecular docking and mechanism of action studies.

Introduction from Guest Editors to Special Issue "Magnetism in Chemistry".

Magnetism in a chemical compound is the macroscopic result of the couplings of the spins of electrons within in it [...].

Introduction from Guest Editors to Special Issue "Multi-Metallic Systems: From Strong Cooperative Bonds to Weak M-M Interactions".

As is known, the chemical elements called metals make up the majority of all the chemical elements included in the periodic table of D [...].

Review on Magnetism in Catalysis: From Theory to PEMFC Applications of 3d Metal Pt-Based Alloys.

The relationship between magnetism and catalysis has been an important topic since the mid-20th century. At present time, the scientific community is well aware that a full comprehension of this relationship is required to face modern challenges, such as the need for clean energy technology. The successful use of (para-)magnetic materials has already been corroborated in catalytic processes, such as hydrogenation, Fenton reaction and ammonia synthesis. These catalysts typically contain transition metals from the first to the third row and are affected by the presence of an external magnetic field. Nowadays, it appears that the most promising approach to reach the goal of a more sustainable future is via ferromagnetic conducting catalysts containing open-shell metals (i.e., Fe, Co and Ni) with extra stabilization coming from the presence of an external magnetic field. However, understanding how intrinsic and extrinsic magnetic features are related to catalysis is still a complex task, especially when catalytic performances are improved by these magnetic phenomena. In the present review, we introduce the relationship between magnetism and catalysis and outline its importance in the production of clean energy, by describing the representative case of 3d metal Pt-based alloys, which are extensively investigated and exploited in PEM fuel cells.

Reduction Rate of 1-Phenyl Phospholane 1-Oxide Enhanced by Silanol Byproducts: Comprehensive DFT Study and Kinetic Modeling Linked to Reagent Design.

Important stoichiometric transformations like Wittig and Appel reactions have been implemented in a catalytic fashion in the past decade. The phosphine oxide generated in situ can be reintroduced as phosphine into the catalytic cycle using mild and selective silane reagents (redox-driven catalysis). While the field of experimental investigation has been fully expanding in the past decade, theoretical studies are still sparse. In this present work, density functional theory (DFT) has been used to characterize the free energy surfaces of the reduction of 1-phenyl phospholane 1-oxide with four different silanes. Found stationary points have been studied in-depth to highlight mechanistic peculiarities, like the effect of substituents at the silicon center and the parallel and competitive reactivity between the precursor silanes and their semioxidized byproducts. Calculated thermodynamic parameters in combination with "real" values for concentrations have been used in the formulation of rate equations for simple bimolecular and monomolecular steps of the mechanism. The deterministic integration concentrations versus time of such rate equations led to a realistic description of the systems under study and paved the way to strategic and rational design of new silanes with increased reactivity.

Ferromagnetic ligand holes in cobalt perovskite electrocatalysts as an essential factor for high activity towards oxygen evolution.

The definition of the interplay between chemical composition, electro-magnetic configuration and catalytic activity requires a rational study of the orbital physics behind active materials. Apart from Coulomb forces, quantum spin exchange interactions (QSEI) are part of the potentials that differentiate the activity of magnetic oxides, strongly correlated electrocatalysts, in electron transfer reactions. Ferromagnetic (FM) cobalt oxides can show low overpotentials for the oxygen evolution reaction (OER) and the La1-XSrXCoO3-δ (0 ≤ X ≤ 1) family of perovskites is good ground to gain understanding of the electronic interactions in strongly correlated catalysts. In this case, Sr-doping raises the OER activity and the conductivity and increases FM spin moments. The efficiency of electrocatalysts based on Earth-abundant 3d-transition metals correlates with the interrelated factors: mild-bonding energies, the reduction of the electronic repulsions because of the QSEI in the open-shells, and enhanced spin delocalization in FM ordering. The reason for the outstanding OER activity of SrCoO3-δ is the accumulation of FM holes in the 3d-2p bonds, including the ligand orbitals, thus facilitating spin-selected charge transport and production of triplet O2 moieties from the oxidation of diamagnetic precursors. Spin-polarized oxygen atoms in the lattice can participate in O-O coupling and release of O2 in a Mars-Van Krevelen mechanistic fashion. We show that the stabilizing FM QSEI decrease the adsorption and activation energies during oxygen evolution and spin-dependent potentials are one of the factors that govern the catalytic activity of magnetic compositions: spintro-catalysis.

Shedding light on the nature of the catalytically active species in photocatalytic reactions using Bi2O3 semiconductor.

The importance of discovering the true catalytically active species involved in photocatalytic systems allows for a better and more general understanding of photocatalytic processes, which eventually may help to improve their efficiency. Bi2O3 has been used as a heterogeneous photocatalyst and is able to catalyze several synthetically important visible-light-driven organic transformations. However, insight into the operative catalyst involved in the photocatalytic process is hitherto missing. Herein, we show through a combination of theoretical and experimental studies that the perceived heterogeneous photocatalysis with Bi2O3 in the presence of alkyl bromides involves a homogeneous BinBrm species, which is the true photocatalyst operative in the reaction. Hence, Bi2O3 can be regarded as a precatalyst which is slowly converted in an active homogeneous photocatalyst. This work can also be of importance to mechanistic studies involving other semiconductor-based photocatalytic processes.

Separating Enthalpic, Configurational, and Solvation Entropic Components in Host-Guest Binding: Application to Cucurbit[7]uril Complexes through a Full In Silico Approach via Water Nanodroplets.

Cucurbiturils are a family of supramolecular hosts obtained by condensation of glycoluril and formaldehyde. Cucurbit[7]uril, CB[7], is the most prominent member of the family for its biomolecular interest, arising from its mild solubility in water and for its strong binding with a large variety of guests containing nonpolar fragments such as adamantanes and ferrocene. For instance, CB[7] encapsulates diamantane diammonium iodide with an attomolar dissociation constant, a value unmatched even in natural encapsulation processes. Computational chemistry has been extensively employed to describe the enthalpic-entropic compensation principle of the molecular recognition process of cucurbituril hosts, but the synergistic contribution of experimental data is required for accurate results to be obtained. This paper proposes the first fully theoretical model able to reconcile the calculated thermodynamics of the complexation process with the experimental data obtained by calorimetry (ITC) for cucurbit[7]uril. The model allows the isolation and estimation of all of the enthalpic and entropic contributions coming from solute and solvent alike to the whole host-guest binding event and enables the straightforward calculation of the contribution of the solvation entropy to the binding.

Magnetism and Heterogeneous Catalysis: In Depth on the Quantum Spin-Exchange Interactions in Pt3M (M = V, Cr, Mn, Fe, Co, Ni, and Y)(111) Alloys.

Bimetallic Pt-based alloys have drawn considerable attention in the last decades as catalysts in proton-exchange membrane fuel cells (PEMFCs) because they closely fulfill the two major requirements of high performance and good stability under operating conditions. Pt3Fe, Pt3Co, and Pt3Ni stand out as major candidates, given their good activity toward the challenging oxygen reduction reaction (ORR). The common feature across catalysts based on 3d-transition metals and their alloys is magnetism. Ferromagnetic spin-electron interactions, quantum spin-exchange interactions (QSEIs), are one of the most important energetic contributions in allowing milder chemisorption of reactants onto magnetic catalysts, in addition to spin-selective electron transport. The understanding of the role played by QSEIs in the properties of magnetic 3d-metal-based alloys is important to design and develop novel and effective electrocatalysts based on abundant and cheap metals. We present a detailed theoretical study (via density functional theory) on the most experimentally explored bimetallic alloys Pt3M (M = V, Cr, Mn, Fe, Co, Ni, and Y)(111). The investigation starts with a thorough structural study on the composition of the layers, followed by a comprehensive physicochemical description of their resistance toward segregation and their chemisorption capabilities toward hydrogen and oxygen atoms. Our study demonstrates that Pt3Fe(111), Pt3Co(111), and Pt3Ni(111) possess the same preferential multilayered structural organization, known for exhibiting specific magnetic properties. The specific role of QSEIs in their catalytic behavior is justified via comparison between spin-polarized and non-spin-polarized calculations.

Diastereodivergent Enantioselective [8 + 2] Annulation of Tropones and Enals Catalyzed by N-Heterocyclic Carbenes.

N-Heterocyclic carbene catalysts are used for the first time to mediate asymmetric [8 + 2] cycloadditions of enals with tropones. The kinetic [8 + 2] cis-cycloadducts can be epimerized to their trans analogues by simply using increased amounts of base and longer reaction times. Substituted tropones are also tolerated, and the cycloaddition products can be derivatized by hydrogenation or methanolysis. The main stereochemical features of the process have been rationalized by microkinetic modeling based on the results of DFT calculations.

Are homoleptic complexes of ethylene with group 12 metals isolable in solution? A DFT study.

Ethylene efficiently binds late transition metals of groups 10 and 11. In spite of their reactivity, homoleptic compounds of formula [M-(η2-C2H4)3]n+ (with n = 0,1) have been isolated in solution and solid state and characterized spectroscopically throughout the last 50 years with metals from groups 10 and 11. X-ray diffraction studies proved that such homoleptic adducts adopt planar "wheel" structures where ethylene moieties lies flat in the same plane both in group 10 and 11. These experimental findings were also confirmed by several in-depth computational investigations carried out to understand the bond pattern of such peculiar structures. Homoleptic complexes of group 10 and 11 metals with ethylene are normally obtained in poorly coordinating solvents (like CH2Cl2 or light petroleum) saturated with ethylene to increase the stability of such species in solution. In the case of coinage metals, Cu(I), Ag(I) and Au(I), weakly coordinating fluorinated counter-ions (like SbF6-) succeeded in stabilize the ethylene adducts, but, curiously, no analogous success has been reported for Zn(II), Cd(II), and Hg(II). Isoelectronic congeners along group 12 are still elusive, however, and, to our knowledge, full experimental and theoretical characterizations are still missing. This manuscript focuses on the theoretical study of the thermodynamic stability and properties of homoleptic complexes of ethylene with metals from group 12 in comparison with those from groups 10 and 11.

Antimicrobial properties of highly fluorinated tris(pyrazolyl)borates.

Highly fluorinated tris(pyrazolyl)borates were tested for their antimicrobial activity against various bacterial species. Both the silver(I) tris(pyrazolyl)borate [HB(3,5-(CF(3))(2)Pz)(3)]Ag(THF) (THF=tetrahydrofuran) and the sodium analog [HB(3,5-(CF(3))(2)Pz)(3)]Na(THF) appeared highly effective at inhibiting the growth of two different species of Gram-positive bacteria (i.e. being 12 and 21 fold more effective, respectively, (on a molar basis, based on the minimum inhibitory concentrations) against Staphylococcus aureus than silver sulfadiazine, a currently used silver antimicrobial). This suggests that the ligand portion of these molecules is responsible for the observed high effectiveness against the Gram-positive species. Furthermore, it appeared that the fluorinated substituents on the tris(pyrazolyl)borate were important for this high level of growth inhibition. Against two species of Gram-negative bacteria, including Pseudomonas aeruginosa, the fluorinated silver(I) tris(pyrazolyl)borate exhibited a moderate level of growth inhibition (similar to that of silver sulfadiazine), while the sodium analog showed very little ability to inhibit growth, indicating that for the Gram-negative species, the apparent responsible antimicrobial portion is the silver ion.

Antimicrobial properties of highly fluorinated silver(I) tris(pyrazolyl)borates.

Highly fluorinated tris(pyrazolyl)borate ligand [HB(3,5-(CF3)2Pz)3]- has been used in the isolation of air- and light-stable silver complex, [HB(3,5-(CF3)2Pz)3]Ag(OSMe2). It is a monomeric tetrahedral silver complex with an O-bonded dimethylsulfoxide ligand. The silver adduct [HB(3,5-(CF3)2Pz)3]Ag(OSMe2) and the related [HB(3,5-(CF3)2Pz)3] Ag(THF) (where OSMe2 = dimethyl sulfoxide; THF = tetrahydrofuran) show good antibacterial activity, and their antimicrobial efficacy against Staphylococcus aureus is greater than those of AgNO3 and silver sulfadiazine.

Organometallic wheels based on coinage metal ions and norbornene: syntheses and structural characterization of [M(norbornene)(3)][SbF(6)] (M = Au, Ag, Cu).

Three closely related organometallic "spoke-wheel" complexes featuring coinage metal ions, Au(I), Ag(I), and Cu(I), bonded to three norbornene molecules in trigonal planar fashion have been isolated and completely characterized using several methods including X-ray crystallography.

A non-classical copper carbonyl on a tri-alkene hydrocarbon support.

Two rare copper complexes, a tri-alkene adduct [Cu(ttt-cdt)(FSbF(5))] and a non-classical carbon monoxide complex [Cu(ttt-cdt)(CO)][SbF(6)] with a high CO stretching frequency ([small nu, Greek, macron](CO) = 2160 cm(-1)), have been isolated using trans,trans,trans-1,5,9-cyclododecatriene (ttt-cdt) ligand.

Syntheses, structures, and reactivity of new pentamethylcyclopentadienyl-rhodium(III) and -iridium(III) 4-acyl-5-pyrazolonate complexes.

New [CpM(Q)Cl] complexes (M = Rh or Ir, Cp = pentamethylcyclopentadienyl, HQ = 1-phenyl-3-methyl-4R(C=O)-pyrazol-5-one in general, in detail HQ(Me), R = CH(3); HQ(Et), R = CH(2)CH(3); HQ(Piv), R = CH(2)-C(CH(3))(3); HQ(Bn), R = CH(2)-(C(6)H(5)); HQ(S), R = CH-(C(6)H(5))(2)) have been synthesized from the reaction of [CpMCl(2)](2) with the sodium salt, NaQ, of the appropriate HQ proligand. Crystal structure determinations for a representative selection of these [CpM(Q)Cl] compounds show a pseudo-octahedral metal environment with the Q ligand bonded in the O,O'-chelating form. In each case, two enantiomers (S(M)) and (R(M)) arise, differing only in the metal chirality. The reaction of [CpRh(Q(Bn))Cl] with MgCH(3)Br produces only halide exchange with the formation of [CpRh(Q(Bn))Br]. The [CpRh(Q)Cl] complexes react with PPh(3) in dichloromethane yielding the adducts CpRh(Q)Cl/PPh(3) (1:1) which exist in solution in two different isomeric forms. The interaction of [CpRh(Q(Me))Cl] with AgNO(3) in MeCN allows generation of [CpRh(Q(Me))(MeCN)]NO(3).3H(2)O, whereas the reaction of [CpRh(Q(Me))Cl] with AgClO(4) in the same solvent yields both [CpRh(Q(Me))(H(2)O)]ClO(4) and [CpRh(Cl)(H(2)O)(2)]ClO(4); the H(2)O molecules derive from the not-rigorously anhydrous solvents or silver salts.