σ versus π-radical: Tuning the electronic nature of neutral carbon (I) compounds with three non-bonding electrons

The bonding and reactivity of the hypo-coordinated compounds with one, two, and four non-bonding electrons namely, carbon-centered free radical, carbenes, and carbones were well earlier established. Here, we report stability, bonding and reactivity of compounds RCL, where R is one-electron donor group (R =  CH₃ ( a ),  CHO ( b ), and  NO₂ ( c )) and L is two-electron donor ligand (L = cAAC ( 1 ), CO ( 2 ), NHC ( 3 ) and PMe₃ ( 4 )), having three non-bonding electrons. The ground states of molecules exist in a doublet with a lone pair of electrons and an unpaired electron at the central carbon atom (C1). The spin hops over from π- to σ-type orbitals is observed as the π-acceptor strength of the donor ligand increases. The replacement of the methyl group by  CHO and  NO₂ indicate that the cAAC and  CHO substituted compounds gives a σ-radical except in compound 2c . These molecules show very high proton affinity and exothermic reaction energy for the hydrogen atom addition indicating dual reactivity namely, radical and lone pair reactivity.     

No dense metrizable Gδ-subspaces in butterfly semi-metrizable Baire spaces

A class of Baire spaces, which contains many known examples and variations thereof, is described and it is shown that no space in this class contains a dense metrizable G_δ-subspace. This gives a class of semi-metrizable spaces which are not σ-spaces. We discuss the existence of Lindelöf semi-metrizable spaces which are not σ-spaces. This is of interest since the only known examples require the use of CH.     

分子间的非共价相互作用：σ-穴键和π-穴键

第四到第七主族元素以及惰性气体元素可以作为电子受体位点形成分子间吸引性的非共价键合作用。这些电子受体位点,即缺电子密度的位点,大多情况下具有正的分子表面静电势,可以将其分为2类。沿着σ共价键键轴延伸方向原子的外围中心具有正的分子表面静电势的区域称之为σ-穴。而垂直于分子σ-骨架平面具有正的分子表面静电势区域称之为π-穴。σ-穴和π-穴与富电性位点之间吸引性的相互作用分别称之为σ-穴键和π-穴键。σ-穴键倾向于180°,而π-穴键倾向于90°。按照元素周期表族的名称,σ-穴键又分为碳素键、氮素键、氧素键、卤键、惰素键等。可见流行的卤键只是σ-穴键的一个子集。π-穴键分类显得复杂些,可简单分为单原子和多原子π-穴键。     

Triple B≡B bond: from a perfect Lewis structure to a dominant π-back-donation. The need for a reference point

Abstract

Coordination of a B₂ fragment by two σ-donor ligands could lead to complexes with a formal triple B≡B bond L→B≡B←L. Formation of L-B σ-bond leads to excess electrons around the B₂ central fragment. A subsequent direct π-charge transfer from B≡B moiety to the ligands L is a necessary condition for incorporation of BB fragment to the conjugated LBBL system. Quantum-chemical calculations (DFT, CCD, and CAS) show that the stabilization of a linear L-BB-L structure is possible but is accompanied by lowering of the B-B bond order. The ammonia-boryne structure H3N→BB←NH₃, which is studied as a model system, shows a perfect triple BB fragment relative to other LBBL adducts. The comparison of the conjugation between the B₂ fragment and two types of σ-donor ligands, with or without π-back-donation, provides an indication of the character of BB multiple bond. Three studied boryne molecules are calculated to have a high barrier for dissociation XXBBXX→XX?+?BBXX, yet a high reactivity of these compounds is indicated by the low-lying excited states of borynes (ΔE_S0-S1<1.5?eV). The largest gap ΔE_S0-S1～2.6?eV is calculated for the room temperature stable bis-NHC-boryne.     

Synthesis of fluspidine via asymmetric NaBH4 reduction of silicon enolates of β-keto esters

Asymmetric NaBH₄ reduction catalyzed by the Co(II) complex of a chiral diamidine-type sp²N ligand, Naph-diPIM-dioxo-iPr, was successfully applied to 3-silyloxycinnamate substrates without over-reduction, giving quantitatively 3-silyloxy-3-arylpropionates with an enantiomer ratio of up to 99:1. The high utility was confirmed on a 30-g scale using 0.1?mol% catalyst. Both Z and E substrates could be converted to a single enantiomeric product by changing the ligand chirality. The relationship between the Z/E stereochemistry and the absolute configuration of the 1,4-reduction product provided important information about the mechanism underlying enantioface selection. Combination of the asymmetric catalysis with two other key steps, Suzuki coupling with an N-protected tetrahydropyridine boronic acid derivative and intramolecular bromo etherification, realized an efficient synthetic route to both enantiomers of fluspidine. The new strategy permits the introduction of substituents on the two aryl groups and piperidine ring, allowing for structural variations toward the development of higher performance σ1 receptor antagonists.     

Cesium-Fluoride-Promoted Synthesis of Stable Organocesium Reagents and Their Ambident Reactivities with Arynes

Described are the diverse reactivities of novel, stable, ambident thio-organocesium reagents (bearing electron withdrawing groups) against benzynes. Reactions at reflux temperature predominantly led to the generation of various functionalized stable sulfonium ylides and at 40 °C the same reaction underwent direct c-arylation. Furthermore, lack of internal hydrogen on the cesium reagent helped to produce different ortho-bifunctional arynes in both the reactions. Interestingly, depending on the reactivities of substrates, the one-pot tri-component procedure generated either ylides or σ-bond insertion products.     

Metal Centers as Nucleophiles: Oxymoron of Halogen Bond-Involving Crystal Engineering

This review highlights recent studies discovering unconventional halogen bonding (HaB) that involves positively charged metal centers. These centers provide their filled d-orbitals for HaB, and thus behave as nucleophilic components toward the noncovalent interaction. This role of some electron-rich transition metal centers can be considered an oxymoron in the sense that the metal is, in most cases, formally cationic; consequently, its electron donor function is unexpected. The importance of Ha⋅⋅⋅d-[M] (Ha=halogen; M is Group 9 (Rh, Ir), 10 (Ni, Pd, Pt), or 11 (Cu, Au)) interactions in crystal engineering is emphasized by showing remarkable examples (reported and uncovered by our processing of the Cambridge Structural Database), where this Ha⋅⋅⋅d-[M] directional interaction guides the formation of solid supramolecular assemblies of different dimensionalities.     

Embeddings and frames of function spaces

For every Tychonoff space X we denote by Cp(X) the set of all continuous real-valued functions on X with the pointwise convergence topology, i.e., the topology of subspace of RX. A set P is a frame for the space Cp(X) if Cp(X)⊂P⊂RX. We prove that if Cp(X) embeds in a σ-compact space of countable tightness then X is countable. This shows that it is natural to study when Cp(X) has a frame of countable tightness with some compactness-like property. We prove, among other things, that if X is compact and the space Cp(X) has a Lindelöf frame of countable tightness then t(X)?ω. We give some generalizations of this result for the case of frames as well as for embeddings of Cp(X) in arbitrary spaces.     

Hierarchical Synthesis,Structure, and Photophysical Properties of Gallium- and Ruthenium-Porphyrins with Axially Bonded Azo Ligands

The hierarchical synthesis of three porphyrin and four bisporphyrin derivatives is presented. This strategy relies on the incorporation of linkers based on azo moieties appended with pyridyl and/or acetylenic groups that facilitate axial coordination to Ga- and Ru-metalloporphyrins. These porphyrinic systems allow for a quantitative analysis of the effects of diamagnetic anisotropy (DA) by using ¹H NMR spectroscopic and X-ray crystallographic analyses. A simple power-law relationship between the proton chemical shift and the distance from the porphyrin core is experimentally outlined, which confirms previous theoretical predictions and shows that the limit of DA is about 2 nm. Photophysical properties of the azo-linked porphyrins are analyzed by UV/Vis spectroscopy, showing that significant cis–trans isomerization is not observed for azo ligands bound only to Ga-porphyrins. Incorporation of Ru-porphyrins to an azo ligand facilitates photoswitching behavior, but the process faces competition from decarbonylation of the Ru-porphyrin, and appreciable switching is only documented for GaL1Ru .     

Counter-examples of regularity behavior for σ-evolution equations

In this paper, we mainly discuss the infinite loss of regularity and μ-loss for a σ-evolution type model with oscillating in time coefficients. On the one hand, an explicit counter-example has been constructed in the frequency space to show the precise infinite loss of regularity. On the other hand, due to the finite propagation speed property for σ∈(0,1], we construct the counter-example of a sequence of solutions in R by applying state of art techniques.