σ‐Aromaticity in an Unsaturated Ring: Osmapentalene Derivatives Containing a Metallacyclopropene Unit

In general, aromaticity can be clarified as π‐ and σ‐aromaticity according to the type of electrons with major contributions. The traditional π‐aromaticity generally describes the π‐conjugation in fully unsaturated rings whereas σ‐aromaticity may stabilize fully saturated rings with delocalization caused by σ‐electron conjugation. Reported herein is an example of σ‐aromaticity in an unsaturated three‐membered ring (3 MR), which is supported by experimental observations and theoretical calculations. Specifically, when the 3 MR in cyclopropaosmapentalene is cleaved by ethane through two isodesmic reactions, both of them are highly endothermic (+29.7 and +35.0 kcal mol^?1). These positive values are in sharp contrast to the expected exothermicity, thus indicating aromaticity in the 3 MR. Further nucleus‐independent chemical shift and anisotropy of the current‐induced density calculations reveal the nature of σ‐aromaticity in the unsaturated 3 MR.     

Generating and Trapping Metalla‐N‐Heterocyclic Carbenes

By means of a combined experimental and theoretical approach, the electronic features and chemical behavior of metalla‐N‐heterocyclic carbenes (MNHCs, N‐heterocyclic carbenes containing a metal atom within the heterocyclic skeleton) have been established and compared with those of classical NHCs. MNHCs are strongly basic (proton affinity and pK_a values around 290 kcal mol^?1 and 36, respectively) with a narrow singlet–triplet gap (around 23 kcal mol^?1). MNHCs can be generated from the corresponding metalla‐imidazolium salts and trapped by addition of transition‐metal complexes affording the corresponding heterodimetallic dicarbene derivatives, which can serve as carbene transfer agents.     

Investigation into the Regiochemistry of 1,3‐Dipolar Cycloaddition of C,N‐Diphenyl Nitrone with Some Vinyl Sulfoximines as Dipolarophile: Theoretical Studies

The regiochemistry of 1,3‐dipolar cycloaddition reactions of C,N‐diphenyl nitrone with some vinyl sulfox‐ imines as dipolarophile was investigated using density functional theory (DFT)‐based reactivity indexes and activation energy calculations at B3LYP/6‐31G(d) level of theory. Analysis of the geometries and bond orders (BOs) at the TS structures associated with the different reaction pathways shows that these 1,3‐dipolar cycloaddition reactions occur via an asynchronous concerted mechanism. Analysis of the local electrophilicity and nucleophilicity indexes permits an interpretation about the regioselectivity of these 1,3‐dipolar cycloaddition reactions. The theoretical results obtained in the work clearly predict the regiochemistry of the isolated cycloadducts and agree to experimental outcomes.     

Investigation into the Regiochemistry of Some Pyrazoles Derived from 1,3‐Dipolar Cycloaddition of Methyl Methacrylate with Some Nitrilimines: A Combined Theoretical and Experimental Study

1,3‐Dipolar cycloaddition between methyl methacrylate as dipolarophile and some nitrilimines which were generated in situ afforded the new pyrazoles. The regiochemistry and reactivity of these reactions has been investigated on the basis of density functional theory (DFT)‐based reactivity indexes and activation energy calculations. The theoretical ¹³C NMR chemical shifts of the cycloadducts which were obtained by GIAO method were comparable with the observed values.     

Effect of Sodium Cation on Metallacycle β‐Hydride Elimination in CO2–Ethylene Coupling to Acrylates

The catalytic conversion of carbon dioxide and olefins into acrylates has been a long standing target, because society attempts to synthesize commodity chemicals in a more economical and sustainable fashion. Although nickel complexes have been known to successfully couple CO₂ and ethylene for decades, a key β‐hydride elimination step has proven a major obstacle to the development of a catalytic process. Recent studies have shown that Lewis acid additives can be used to create a lower‐energy pathway for β‐hydride elimination and facilitate a low number of catalytic turnovers. However, the exact manner, in which the Lewis acid promotes β‐hydride elimination remains to be elucidated. Herein, we describe the kinetic and thermodynamic role that commercially relevant and weakly Lewis acidic sodium salts play in promoting β‐hydride elimination from nickelalactones synthesized from CO₂ and ethylene. This process is compared to a non‐Lewis acid promoted pathway, and DFT calculations were used to identify differences between the two systems. The sodium‐free isomerization reaction gave a rare CO₂‐derived β‐nickelalactone complex, which was structurally characterized.     

Non‐Pincer‐Type Mononuclear Scandium Alkylidene Complexes: Synthesis,Bonding, and Reactivity

The first non‐pincer‐type mononuclear scandium alkylidene complexes were synthesized and structurally characterized. These complexes exhibited short Sc?C bond lengths and even one of the shortest reported to date (2.1134(18) Å). The multiple character of the Sc?C bond was highlighted by a DFT calculation. This was confirmed by experimental reactivity study where the complex underwent [2+1] cycloaddition with elemental selenium and [2+2] cycloaddition with imine. DFT calculation also revealed a strong nucleophilic behavior of the alkylidene complex that was experimentally demonstrated by the C?H bond activation of phenylacetylene.     

Spontaneous Dimerization of Allenes in Situ: An Efficient Synthesis of Substituted 1,2‐Dimethylenecyclobutanes with High Regio‐ and Stereoselectivities

An intermolecular [2+2] cycloaddition reaction for the synthesis of 1,2‐dimethylenecyclobutane derivatives from the commercially available starting materials aryl acetylenes, nBuLi, formamides, and trimethylsilyl cyanide (TMSCN) has been achieved. This reaction displays high regio‐ and stereoselectivities due to the captodative effect. The mechanism of the reaction has been investigated by the deuterium labeling experiments and DFT calculations.     

Synthesis and Reactivity Comparisons of 1‐Methyl‐3‐Substituted Cyclopropene Mini‐tags for Tetrazine Bioorthogonal Reactions

Substituted cyclopropenes have recently attracted attention as stable “mini‐tags” that are highly reactive dienophiles with the bioorthogonal tetrazine functional group. Despite this interest, the synthesis of stable cyclopropenes is not trivial and their reactivity patterns are poorly understood. Here, the synthesis and comparison of the reactivity of a series of 1‐methyl‐3‐substituted cyclopropenes with different functional handles is described. The rates at which the various substituted cyclopropenes undergo Diels–Alder cycloadditions with 1,2,4,5‐tetrazines were measured. Depending on the substituents, the rates of cycloadditions vary by over two orders of magnitude. The substituents also have a dramatic effect on aqueous stability. An outcome of these studies is the discovery of a novel 3‐amidomethyl substituted methylcyclopropene tag that reacts twice as fast as the fastest previously disclosed 1‐methyl‐3‐substituted cyclopropene while retaining excellent aqueous stability. Furthermore, this new cyclopropene is better suited for bioconjugation applications and this is demonstrated through using DNA templated tetrazine ligations. The effect of tetrazine structure on cyclopropene reaction rate was also studied. Surprisingly, 3‐amidomethyl substituted methylcyclopropene reacts faster than trans‐cyclooctenol with a sterically hindered and extremely stable tert‐butyl substituted tetrazine. Density functional theory calculations and the distortion/interaction analysis of activation energies provide insights into the origins of these reactivity differences and a guide to the development of future tetrazine coupling partners. The newly disclosed cyclopropenes have kinetic and stability advantages compared to previously reported dienophiles and will be highly useful for applications in organic synthesis, bioorthogonal reactions, and materials science.     

Reaction of N‐Heterocyclic Silylenes with Thioketone: Formation of Silicon–Sulfur Three (Si‐C‐S)‐ and Five (Si‐C‐C‐C‐S)‐Membered Ring Systems

Three‐ and five‐membered rings that bear the (Si‐C‐S ) and (Si‐C‐C‐C‐S ) unit have been synthesized by the reactions of L SiCl ( 1 ; L =PhC(NtBu)₂) and L′ Si ( 2 ; L′ =CH{(C?CH₂)(CMe)(2,6‐iPr₂C₆H₃N)₂}) with the thioketone 4,4′‐bis(dimethylamino)thiobenzophenone. Treatment of 4,4′‐bis(dimethylamino)thiobenzophenone with L SiCl at room temperature furnished the [1+2]‐cycloaddition product silathiacyclopropane 3 . However, reaction of 4,4′‐bis(dimethylamino)thiobenzophenone with L′ Si at low temperature afforded a [1+4]‐cycloaddition to yield the five‐membered ring product 4 . Compounds 3 and 4 were characterized by NMR spectroscopy, EIMS, and elemental analysis. The molecular structures of 3 and 4 were unambiguously established by single‐crystal X‐ray structural analysis. The room‐temperature reaction of 4,4′‐bis(dimethylamino)thiobenzophenone with L′ Si resulted in products 4 and 5 , in which 4 is the dearomatized product and 5 is formed under the 1,3‐migration of a hydrogen atom from the aromatic phenyl ring to the carbon atom of the C? S unit. Furthermore, the optimized structures of probable products were investigated by using DFT calculations.     

A Metal‐Bridged Tricyclic Aromatic System: Synthesis of Osmium Polycyclic Aromatic Complexes

Aromaticity is one of the most important concepts in organic chemistry. A variety of metalla‐aromatic compounds have been recently prepared and in most of those examples, the metal participates only in a monocyclic ring. In contrast, metal‐bridged bicyclic aromatic molecules, in which a metal is shared between two aromatic rings, have been less developed. Herein, we report the first metal‐bridged tricyclic aromatic system, in which the metal center is shared by three aromatic five‐membered rings. These metalla‐aromatics are formed by reaction between osmapentalyne and arene nucleophiles. Experimental results and theoretical calculations reveal that the three five‐membered rings around the osmium center are aromatic. In addition, the broad absorption bands in the UV/Vis absorption spectra of these novel aromatic systems cover almost the entire visible region. This straightforward synthetic strategy may be extended to the synthesis of other metal‐bridged polycyclic aromatics.     

Five‐Membered Cyclic Metal Carbyne: Synthesis of Osmapentalynes by the Reactions of Osmapentalene with Allene,Alkyne, and Alkene

The synthesis of small cyclic metal carbynes is challenging due to the large angle strain associated with the highly distorted nonlinear triple bonds. Herein, we report a general route for the synthesis of five‐membered cyclic metal carbyne complexes, osmapentalynes, by the reactions of an osmapentalene derivative with allene, alkyne, and alkene. Experimental observations and theoretical calculations document the aromaticity in the fused five‐membered rings of osmapentalynes. The realization of transforming osmapentalene to osmapentalyne through this general route would not only allow further exploration of metallapentalyne chemistry but also show promising applications of this novel aromatic system with broad absorption band and high molar absorption coefficient.     

Cage‐like Copper(II) Silsesquioxanes: Transmetalation Reactions and Structural,Quantum Chemical,and Catalytic Studies

The transmetalation of bimetallic copper–sodium silsesquioxane cages, namely, [(PhSiO_1.5)₁₀(CuO)₂(NaO_0.5)₂] (“Cooling Tower”; 1 ), [(PhSiO_1.5)₁₂(CuO)₄(NaO_0.5)₄] (“Globule”; 2 ), and [(PhSiO_1.5)₆(CuO)₄(NaO_0.5)₄(PhSiO_1.5)₆] (“Sandwich”; 3 ), resulted in the generation of three types of hexanuclear cylinder‐like copper silsesqui‐ oxanes, [(PhSiO_1.5)₁₂(CuO)₆(C₄H₉OH)₂(C₂H₅OH)₆] ( 4 ), [(PhSiO_1.5)₁₂(CuO)₆(C₄H₈O₂)₄(PhCN)₂(MeOH)₄] ( 5 ), and [(PhSiO_1.5)₁₂(CuO)₆(NaCl)(C₄H₈O₂)₁₂(H₂O)₂] ( 6 ). The products show a prominent “solvating system–structure” dependency, as determined by X‐ray diffraction. Topological analysis of cages 1 – 6 was also performed. In addition, DFT theory was used to examine the structures of the Cooling Tower and Cylinder compounds, as well as the spin density distributions. Compounds 1 , 2 , and 5 were applied as catalysts for the direct oxidation of alcohols and amines into the corresponding amides. Compound 6 is an excellent catalyst in the oxidation reactions of benzene and alcohols.     

Reactivity of Single‐Walled Carbon Nanotubes in the Diels–Alder Cycloaddition Reaction: Distortion–Interaction Analysis along the Reaction Pathway

Diels–Alder cycloaddition is one of the most powerful tools for the functionalization of single‐walled carbon nanotubes (SWCNTs). Density functional theory at the B3‐LYP level of theory has been used to investigate the reactivity of different‐diameter SWCNTs (4–9,5) in Diels–Alder reactions with 1,3‐butadiene; the reactivity was found to decrease with increasing SWCNT diameter. Distortion/interaction analysis along the whole reaction pathway was found to be a better way to explore the reactivity of this type of reaction. The difference in interaction energy along the reaction pathway is larger than that of the corresponding distortion energy. However, the distortion energy plots for these reactions show the same trend. Therefore, the formation of the transition state can be determined from the interaction energy. A lower interaction energy leads to an earlier transition state, which indicates a lower activation energy. The computational results also indicate that the original distortion of the SWCNTs leads to an increase in the reactivity of the SWCNTs.     

Synthesis of Planar Chiral Iridacycles by Cationic Metal π‐Coordination: Facial Selectivity,and Conformational and Stereochemical Consequences

Facial selectivity during the π‐coordination of pseudo‐tetrahedral iridacycles by neutral (Cr(CO)₃), monocationic (Cp*Ru⁺), and biscationic (Cp*Ir²⁺) metal centers was directly influenced by the coulombic imbalance in the coordination sphere of the chelated Ir center. We also showed by using theoretical calculations that the feasibility of the related metallacycles that displayed metallocenic planar chirality was dependent to the presence of an electron‐donating group, such as NMe₂, which contributed to the overall stability of the complexes. When the π‐bonded moiety was the strongly electron‐withdrawing Cp*Ir²⁺ group, the electron donation from NMe₂ resulted in major conformational changes, with a barrier to rotation of about 17 kcal mol^?1 for this group that became spectroscopically diastereotopic (high‐field ¹H NMR spectroscopy). This peculiar property is proposed as a means to introduce a new type of constitutional chirality at the nitrogen center: planar chirality at tertiary aromatic amines.