Synthesis of Azo-Substituted Bicyclo[1.1.1]pentanes (BCPs) via Base-Promoted Halogen Atom Transfer.

Because of the three-dimensional bioisosteric feature, bicyclo[1.1.1]pentylamines (BCPAs) are valuable scaffolds in synthetic chemistry and medicinal chemistry. Here, we report a Halogen Atom Transfer (XAT) mediated radical C-N coupling between C3-iodo-BCPs and diazonium salts in the presence of base. Similarly, a multicomponent reaction (MCR) enables the simultaneous construction of the C-C bond and C-N bond simultaneously. Versatile roles of diazonium salts were also explored.

A 12-Vertex Metallacarborane of Silver(I).

The discovery of ferrocene in 1951 was a significant landmark in the field of organometallic chemistry, and since then, numerous sandwich- or half-sandwich metallic complexes have been reported. However, silver stands as an intriguing exception in this regard, and knowledge of its bonding situation has remained undisclosed. Herein, unprecedented 12-vertex metallacarboranes of Ag(I) (2a and 2b) were synthesized through the reaction of sodium hexamethyldisilazide (NaHMDS) with the mixture of nido-C2B9 carborane anion-supported N-heterocyclic carbene precursors (1a and 1b) and [Ag(PPh3)Cl]4. The X-ray structural analysis of the resulting metallacarboranes revealed a unique "slipped" half-sandwich structure, which is a rarity among cyclopentadienyl analogues. DFT calculations provided insights into the asymmetric π-interactions between the pentagonal C2B3 face and the silver ion.

Nickelacarborane-Supported Bis-N-heterocyclic Carbenes.

Metallacarboranes have attracted significant attention due to their unique properties. Considerable efforts have been made on the reactions around the metal centers or the metal ion itself, while transformations of functional groups of the metallacarboranes have been much less explored. We presented here the formation of imidazolium-functionalized nickelacarboranes (2), their subsequent conversion to nickelacarborane-supported N-heterocyclic carbenoids (NHCs, 3), and the reactivities of 3 toward Au(PPh3)Cl and Se powder, which resulted in the formation of bis-gold carbene complexes (4) and NHC selenium adducts (5). Cyclic voltammetry of 4 shows two reversible peaks, corresponding to the interconversion transformations NiII ↔ NiIII and NiIII ↔ NiIV. Theoretical calculations demonstrated relatively high-lying lone-pair orbitals, weak B-H···H-C interactions between the BH units and the methyl group, and weak B-H···π interactions between the BH groups and the vacant p-orbital of the carbene.

Cyclic Carbonate Synthesis from Epoxides and CO2 Catalyzed by Aluminum-Salen Complexes Bearing a nido-C2B9 Carborane Ligand.

The active and well-designed Schiff base ligands are considered "privileged ligands". The so-called salen ligands, i.e., the tetradentate [O, N, N, O] bis-Schiff base ligands, have also found broad applications in many homogeneous catalytic reactions. Modification of the salen ligands has concentrated on altering the substituents in the phenolate rings and variations in the diamine backbones. Herein, o-carborane-supported salen ligands (2) were designed and prepared. A series of aluminum-salen complexes (3·(sol)2), which were supported by the nido-C2B9 carborane anions, were synthesized. These Al(III) complexes showed high activities (TOF up to 1500 h-1) in catalyzing the cycloaddition of epoxides and CO2 at atmospheric pressure and near room temperature. Complexes 3·(sol)2 are one of the rare examples of Al-based catalysts capable of promoting cycloaddition at 1 bar pressure of CO2. Density functional theory (DFT) studies combined with the catalytic results reveal that the catalytic cycles occur on two axial sites of the Al(III) center.

Sustainable Four-Component Annulation for the Synthesis of 2,3,4,6-Tetraarylpyridines.

A one-pot, four-component annulation of 2,3,4,6-tetraarylpyridines from aromatic aldehydes, methyl ketones, diaryl ethanones, and ammonium acetate is described. The reaction features high functional group compatibility in air under solvent-free conditions without any additive and only water as the nontoxic byproduct, providing a strategy for the facile, economical, and eco-friendly construction of multiaryl-substituted pyridines from simple and readily available reactants.

Catalytic Asymmetric trans-Selective Hydrosilylation of Bisalkynes to Access AIE and CPL-Active Silicon-Stereogenic Benzosiloles.

Chirality widely exists in a diverse array of biologically active molecules and life forms, and the catalytic constructions of chiral molecules have triggered a heightened interest in the fields of chemistry and materials and pharmaceutical sciences. However, the synthesis of silicon-stereogenic organosilicon compounds is generally recognized as a much more difficult task than that of carbon-stereogenic centers because of no abundant organosilicon-based chiral sources in nature. Herein, we reported a highly enantioselective rhodium-catalyzed trans-selective hydrosilylation of silicon-tethered bisalkynes to access chiral benzosiloles bearing a silicon-stereogenic center. This protocol featured with chiral Ar-BINMOL-Phos bearing hydrogen-bond donors as a privileged P-ligand for catalytic asymmetric hydrosilylation that is operationally simple and has 100% atom-economy with good functional group tolerability as well as high enantioselectivity (up to >99:1 er). Benefiting from the trans-selective hydrosilylation with the aid of Rh/Ar-BINMOL-Phos-based asymmetric catalysis, the Si-stereogenic benzosiloles exhibited pronounced aggregation-induced emission (AIE) and circularly polarized luminescence (CPL) activity.

A Stable Cyclic (R2 SnAu)3 Anion Having In-Plane σ-Möbius Aromaticity.

A cyclic (R2 SnAu)3 anion (3- , R2 Sn=2,2,5,5-tetrakis(trimethylsilyl)-1-stannacyclopentane-1,1-diyl) has been synthesized as a stable blue salt with K+ (THF)6 through the reaction of stable dialkylstannylene 1 with R'3 PAuCl (R'=Et, Ph) followed by the reduction with KC8 . Crystallographic and NMR analysis shows that the six-membered (SnAu)3 ring of 3- is planar and highly symmetric with an equal distance of six Au-Sn bonds. A UV/Vis spectrum of 3- in hexane reveals an intense absorption maximum at 598 nm. While cyclic Au3 - with four valence electrons is known as unstable anti-aromatic anion, 3- with three divalent tin ligands is stable σ aromatic anion with an unprecedented Möbius orbital array as predicted by the perturbation MO and CCSD analysis of 3- .

A Simple Metal-Free Cyclization for the Synthesis of 4-Methylene-3-Substituted Quinazolinone and Quinazolinthione Derivatives: Experiment and Theory.

A new series of 3-substituted 4-methylene-quinazolinthiones and 4-methylene-quinazolinones were synthesized in moderate to excellent yield through a simple reaction of 2-aminoacetophenones with isocyanates or isothiocyanates. The reaction shows good tolerance of many important functional groups in the presence of air and water under metal-free conditions. Only water is produced as a coproduct, rendering this "green" methodology a highly versatile and eco-friendly alternative to the existing methods for the construction of the quinazolinone/quinazolinthione framework. We have interpreted the reaction mechanism by use of quantum chemical calculations on the basis of state-of-the-art computational methods SMD-B3LYP-D3(BJ)/BS1//B3LYP/BS1.

Synthesis, structure and DFT calculations of 1,2-N-substituted o-carboranes.

A series of 1,2-N-substituted o-carboranes were obtained. The C-C bond lengths of secondary-amino o-carboranes 3 were compared. The relationship between C-C distances and the electron effects of the benzyl groups was discussed. DFT calculations with and without dispersion energy correction show that significant attractive dispersion forces were present, which arise from the skeletons of the o-carborane cages.

Exceptionally Long C-C Single Bonds in Diamino-o-carborane as Induced by Negative Hyperconjugation.

The synthesis of a series of 1,2-diamino-o-carboranes (1-4) is reported. The molecular structures of these diamino-o-carboranes are remarkable as the inner-cluster C-C bonds are all ultra-long (162.7-193.1 pm) and vary substantially with small variations in the substituents. The results of quantum mechanical investigations suggest that the origin of the bond elongation is significant in-plane negative hyperconjugation of lone pairs of the nitrogen substituents with the σ* orbitals of the C-C bonds in o-carboranes.

Cation-Triggered Stannate(II)/Stannylenoid/Stannylene Conversion.

The reaction of dipotassio-tetrasilan-1,4-diide (4) with anhydrous SnCl2 at low temperature results in the formation of a five-membered cyclic potassio chlorostannate(II) ([(18-C-6)K](1)). By careful cation exchange reactions, it was transformed into the sodium chlorostannylenoid 2 (by using Na2 [B12 Cl12 ]) or into the non-stabilized cyclic bissilylstannylene 3 (through applying Li[Al(OC(CF3 )3 )4 ]). The increasing Lewis basicity of the bissilylstannylene 3 was analyzed by combined methods of DFT calculations and NMR spectroscopy and substantiated by the synthesis of the corresponding iron carbonyl complexes 7 and 8 from the chlorostannate 1 and the stannylene 3, respectively.

Reactions of an Isolable Dialkylsilylene with Aroyl Chlorides. A New Route to Aroylsilanes.

The reactions of isolable dialkylsilylene 1 with aromatic acyl chlorides afforded aroylsilanes 3a-3c exclusively. Aroylsilanes 3a-3c were characterized by ¹H-, 13C-, and 29Si-NMR spectroscopy, high-resolution mass spectrometry (HRMS), and single-crystal molecular structure analysis. The reaction mechanisms are discussed in comparison with related reaction of 1 with chloroalkanes and chlorosilanes.

Reversible Stannylenoid Formation from the Corresponding Stannylene and Cesium Fluoride.

A fluorostannylenoid (Cs+ [R2 SnF]- (9), R2 =(TMS)2 CCH2 CH2 C(TMS)2 ) was prepared by reacting a stable dialkylstannylene (R2 Sn (8), R2 =(TMS)2 CCH2 CH2 C(TMS)2 ) with cesium fluoride at room temperature in THF. While 9 is stable in THF and DME, removal of the solvent leads to the regeneration of stannylene 8. No reaction occurred when 8 was treated with CsF in a hydrocarbon solvent. Addition of dibenzo-21-crown-7 ether to the THF solution of stannylenoid 9 followed by usual workup affords the corresponding crystalline stannylenoid crown ether complex, the X-ray structural analysis of which revealed a fluorine-bridged contact ion-pair structure. The reaction of 9 with excess phenylacetylene gives the corresponding di(phenylethynyl)stannane.

1,3-Diazasilabicyclo[1.1.0]butane with a Long Bridging N-N Bond.

A 1,3-diazasilabicyclo[1.1.0]butane (1) is synthesized as thermally stable crystals by using the cycloaddition reaction of an isolable dialkylsilylene with aziadamantane. The bridge N-N bond length of 1 (1.70 Å) is the longest among those of known N-N singly-bonded compounds, including side-on bridged transition-metal dinitrogen complexes. The compound 1 is intact in air but moisture sensitive. No reaction occurs with hydrogen, even under pressure at 0.5 MPa. Irradiation of 1 with light gives an isomer quantitatively by N-N and adamantyl C-C bond cleavage. The origin of the remarkable N-N bond elongation is ascribed to significant interaction between a Si-C σ* and Ν-Ν π and σ orbitals as determined by DFT calculations of model compounds.

Elusive 2H-1,2-oxasiletes through reactions of an isolable dialkylsilylene with diazocarbonyl compounds.

The reactions of isolable dialkysilylene 1 with 2-diazo-1,2-diphenylethanone and ethyl 2-diazo-2-phenylacetate gave elusive silacycles, 2H-1,2-oxasiletes 2 and 3, respectively, in high yields. Because these reactions occur at low temperatures of ca.-30 °C, initial complexation of the silylene to the carbonyl oxygen of the diazocarbonyl compounds is suggested to trigger dinitrogen elimination followed by cyclization. In contrast, a six-membered cyclic diazo compound 8 and 1-sila-2,3-diazabicyclo[3.3.0]oct-3-ene 10 were obtained in good yields by the reaction of 1 with less reactive ethyl 2-diazo-3-oxo-3-phenylpropanoate 7 and trimethylsilyldiazomethane 9. Molecular structures of 2, 3, 8 and 10 were determined by X-ray crystallography.

Reactions of an isolable dialkylsilylene with aromatic nitriles providing a new type of heterosilole.

The 1 : 2 reactions of isolable dialkylsilylene with nitriles having electron-donating aromatic substituents gave 1,4-diaza-2-siloles with a hitherto-unknown type of ring system, in contrast to the previous studies showing exclusive formation of the corresponding 1,3-diaza-2-siloles; the reactions of with aromatic nitriles bearing electron-withdrawing substituents afforded the latter ring system. The remarkable diversity of the reactions is explained by invoking the corresponding nitrile silaylides as key intermediates whose polarity switches depending on the substituents of nitriles.

Reduction of the dihalocyclopentasilanes. A quest for a homocyclic silylene.

The reduction of dichloro- and dibromo-cyclopentasilanes with C8K was investigated. A potassium silyl anion and a fused tricyclic silane were isolated, respectively. These results indicate that a homocyclic silylene intermediate is generated in the reduction of dibromocyclopentasilane. The trimethylsilyl group is bulky enough to protect the silylene from dimerization, however, it is not a good protecting group for hindering the 1,2-silyl migration.

Synthesis and characterization of heterocyclic disilylchalcogenides.

The reaction of a dipotassium silyl dianion (1) with chalcogenide elements (E) does not afford the corresponding silylchalcogenolates, but allows the generation of a series of heterocyclic disilylchalcogenides (E = S (2), Se (3), Te (4)). Under high temperature, compound 4 can be converted into compound 5, a Te analog of compounds 2 and 3. The compounds were characterized by (1)H, (13)C and (29)Si NMR spectroscopy and high resolution mass spectrometry (HRMS). In addition, X-ray structure analyses were carried out on compounds 2-5. A DFT calculation was also performed.

Phosphole modified pentathienoacene: synthesis, electronic properties and self-assembly.

A series of new ladder π-conjugated materials, phosphole modified pentathienoacene (PO-PTA), are synthesized and characterized. Single-crystal X-ray results demonstrate that methyl-disubstituted PO-PTA forms a face-to-face dimer structure driven by π-π interactions. The investigations of optical properties showed that the oxidized phosphole moiety in this ladder system can effectively narrow the band gap. PO-PTA is a promising building block in π-conjugated polymers and oligomers for optoelectronic applications. The derivative of PO-PTA, obtained by introducing four long alkyl chains, can self-assemble into one-dimensional (1D) fibers based on intermolecular π-π interactions, dipole-dipole interactions and van der Waals interactions. Interestingly, the uniform and well-ordered monolayers were also obtained for PO-PTA derivative on a HOPG (highly oriented pyrolytic graphite) surface.

Novel ladder π-conjugated materials--sila-pentathienoacenes: synthesis, structure, and electronic properties.

A novel series of ladder π-conjugated materials--sila-pentathienoacenes (Si-PTA) are synthesized and characterized. Crystal structures of the compounds show that the length of alkyl chains substituting on the thiophene ring has a significant influence on molecular packing. A densely packed structure with an interfacial distance of about 3.66 Å between the adjacent molecules is observed for the compound with shorter alkyl chains. However, a large interfacial distance (7.99 Å) is obtained for another compound because of the insertion of long alkyl chains between two planes. The investigation of the optical and electrochemical properties shows that the silylene bridge incorporated into the pentathienoacene framework exerts a clear effect on the electronic properties by the σ*-π* conjugation. Although only a slight enhancement is observed for the HOMO levels, with respect to that of pentathienoacene, the LUMO levels are significantly lowered. The observed electronic properties are consistent with the theoretical calculations.