exo-6b2-Methyl-Substituted Pentabenzocorannulene: Synthesis, Structural Analysis, and Properties.

exo-6b2-Methyl-substituted pentabenzocorannulene (exoPBC-Me) was synthesized by the palladium-catalyzed cyclization of 1,2,3-triaryl-1H-cyclopenta[l]phenanthrene. Its bowl-shaped geometry with an sp3 carbon atom in the backbone and a methyl group located at the convex (exo) face was verified by X-ray crystallography. According to DFT calculations, the observed conformer is energetically more favorable than the endo one by 39.9 kcal/mol. Compared to the nitrogen-doped analogs with intact π-conjugated backbones (see the main text), exo-PBC-Me displayed a deeper bowl depth (avg. 1.93 Å), redshifted and broader absorption (250-620 nm) and emission (from 585 to more than 850 nm) bands and a smaller optical HOMO-LUMO gap (2.01 eV). exo-PBC-Me formed polar crystals where all bowl-in-bowl stacking with close π···π contacts is arranged unidirectionally, providing the potential for applications as organic semiconductors and pyroelectric materials. This unusual structural feature, molecular packing, and properties are most likely associated with the assistance of the methyl group and the sp3 carbon atom in the backbone.

Electron Dynamics in Alkane C-H Activation Mediated by Transition Metal Complexes.

Alkanes, ideal raw materials for industrial chemical production, typically exhibit limited reactivity due to their robust and weakly polarized C-H bonds. The challenge lies in selectively activating these C-H bonds under mild conditions. To address this challenge, various C-H activation mechanisms have been developed. Yet, classifying these mechanisms depends on the overall stoichiometry, which can be ambiguous and sometimes problematic. In this study, we utilized density functional theory calculations combined with intrinsic bond orbital (IBO) analysis to examine electron flow in the four primary alkane C-H activation mechanisms: oxidative addition, σ-bond metathesis, 1,2-addition, and electrophilic activation. Methane was selected as the representative alkane molecule to undergo C-H heterolytic cleavage in these reactions. Across all mechanisms studied, we find that the CH3 moiety in methane consistently uses an electron pair from the cleaved C-H bond to form a σ-bond with the metal. Yet, the electron pair that accepts the proton differs with each mechanism: in oxidative addition, it is derived from the d-orbitals; in σ-bond metathesis, it resulted from the metal-ligand σ-bonds; in 1,2-addition, it arose from the π-orbital of the metal-ligand multiple bonds; and in electrophilic activation, it came from the lone pairs on ligands. This detailed analysis not only provides a clear visual understanding of these reactions but also showcases the ability of the IBO method to differentiate between mechanisms. The electron flow discerned from IBO analysis is further corroborated by results from absolutely localized molecular orbital energy decomposition analysis, which also helps to quantify the two predominant interactions in each process. Our findings offer profound insights into the electron dynamics at play in alkane C-H activation, enhancing our understanding of these critical reactions.

Catalytically Relevant Organocopper(III) Complexes Formed through Aryl-Radical-Enabled Oxidative Addition.

Stepwise oxidative addition of copper(I) complexes to form copper(III) species via single electron transfer (SET) events has been widely proposed in copper catalysis. However, direct observation and detailed investigation of these fundamental steps remain elusive owing largely to the typically slow oxidative addition rate of copper(I) complexes and the instability of the copper(III) species. We report herein a novel aryl-radical-enabled stepwise oxidative addition pathway that allows for the formation of well-defined alkyl-CuIII species from CuI complexes. The process is enabled by the SET from a CuI species to an aryl diazonium salt to form a CuII species and an aryl radical. Subsequent iodine abstraction from an alkyl iodide by the aryl radical affords an alkyl radical, which then reacts with the CuII species to form the alkyl-CuIII complex. The structure of resultant [(bpy)CuIII(CF3)2(alkyl)] complexes has been characterized by NMR spectroscopy and X-ray crystallography. Competition experiments have revealed that the rate at which different alkyl iodides undergo oxidative addition is consistent with the rate of iodine abstraction by carbon-centered radicals. The CuII intermediate formed during the SET process has been identified as a four-coordinate complex, [CuII(CH3CN)2(CF3)2], through electronic paramagnetic resonance (EPR) studies. The catalytic relevance of the high-valent organo-CuIII has been demonstrated by the C-C bond-forming reductive elimination reactivity. Finally, localized orbital bonding analysis of these formal CuIII complexes indicates inverted ligand fields in σ(Cu-CH2) bonds. These results demonstrate the stepwise oxidative addition in copper catalysis and provide a general strategy to investigate the elusive formal CuIII complexes.

Efficient conversion of propane in a microchannel reactor at ambient conditions.

The oxidative dehydrogenation of propane, primarily sourced from shale gas, holds promise in meeting the surging global demand for propylene. However, this process necessitates high operating temperatures, which amplifies safety concerns in its application due to the use of mixed propane and oxygen. Moreover, these elevated temperatures may heighten the risk of overoxidation, leading to carbon dioxide formation. Here we introduce a microchannel reaction system designed for the oxidative dehydrogenation of propane within an aqueous environment, enabling highly selective and active propylene production at room temperature and ambient pressure with mitigated safety risks. A propylene selectivity of over 92% and production rate of 19.57 mmol mCu-2 h-1 are simultaneously achieved. This exceptional performance stems from the in situ creation of a highly active, oxygen-containing Cu catalytic surface for propane activation, and the enhanced propane transfer via an enlarged gas-liquid interfacial area and a reduced diffusion path by establishing a gas-liquid Taylor flow using a custom-made T-junction microdevice. This microchannel reaction system offers an appealing approach to accelerate gas-liquid-solid reactions limited by the solubility of gaseous reactant.

A New Series of Sandwich-Type 5,5'-Biterphenylenes: Synthetic Challenge, Structural Uniqueness and Photodynamics.

A new series of biaryls, bi-linear-terphenylenes (BLTPs), were prepared using the tert-butyllithium-mediated cyclization as the key synthetic step. The three-dimensional structures of the studied compounds were verified using X-ray crystallography and DFT calculations. Tetraaryl(ethynyl)-substituted BLTPs are highly crowded molecules, and the internal rotation around the central C-C bond is restricted due to a high barrier (>50 kcal/mol). These structures contain several aryl/terphenylenyl/aryl sandwiches, where the through-space π-π (TSPP) interactions are strongly reflected in the shielding of 1 H NMR chemical shifts, reduction of oxidation potentials, increasing aromaticity of the central six-membered ring and decreasing antiaromaticity of the four-membered rings in a terphenylenyl moiety based on NICS(0) and iso-chemical shielding surfaces. Despite the restricted C-C bond associated intramolecular TSPP interactions for BLTPs in the ground state, to our surprise, the electronic coupling between two linear terphenylenes (LTPs) in BLTPs in the excited state is weak, so that the excited-state behavior is dominated by the corresponding monomeric LTPs. In other words, all BLTPs undergo ultrafast relaxation dynamics via strong exciton-vibration coupling, acting as a blue-light absorber with essentially no emission.

Copper-Carbon Homolysis Competes with Reductive Elimination in Well-Defined Copper(III) Complexes.

Despite the recent advancements of Cu catalysis for the cross-coupling of alkyl electrophiles and the frequently proposed involvement of alkyl-Cu(III) complexes in such reactions, little is known about the reactivity of these high-valent complexes. Specifically, although the reversible interconversion between an alkyl-CuIII complex and an alkyl radical/CuII pair has been frequently proposed in Cu catalysis, direct observation of such steps in well-defined CuIII complexes remains elusive. In this study, we report the synthesis and investigation of alkyl-CuIII complexes, which exclusively undergo a Cu-C homolysis pathway to generate alkyl radicals and CuII species. Kinetic studies suggest a bond dissociation energy of 28.6 kcal/mol for the CuIII-C bonds. Moreover, these four-coordinate complexes could be converted to a solvated alkyl-CuIII-(CF3)2, which undergoes highly efficient C-CF3 bond-forming reductive elimination even at low temperatures (-4 °C). These results provide strong support for the reversible recombination of alkyl radicals with CuII to form alkyl-CuIII species, an elusive step that has been proposed in Cu-catalyzed mechanisms. Furthermore, our work has demonstrated that the reactivity of CuIII complexes could be significantly influenced by subtle changes in the coordination environment. Lastly, the observation of the highly reactive neutral alkyl-CuIII-(CF3)2 species (or with weakly bound solvent molecules) suggests they might be the true intermediates in many Cu-catalyzed trifluoromethylation reactions.

Influence of Ring Strain on the Formation of Rearrangement vs Cyclization Isotwistane Products in the Acyl Radical Reaction of Bicyclo[2.2.2]octanone.

An acyl radical reaction of bicyclo[2.2.2]octenone to yield either rearranged or cyclized isotwistane products is described. The influence of ring strain on the reaction was demonstrated by alternating the sizes of the fused ring in the starting material. DFT calculations showed that the reaction is under thermodynamic control and proceeds via a 5-exo-trig cyclization intermediate, which undergoes either hydrogen-atom transfer (HAT) to give a cyclized product or rearrangement via a twistane intermediate to give a rearranged product.

Synthesis, structural analysis, and properties of highly twisted alkenes 13,13'-bis(dibenzo[a,i]fluorenylidene) and its derivatives.

The rotation of a C = C bond in an alkene can be efficiently accelerated by creating the high-strain ground state and stabilizing the transition state of the process. Herein, the synthesis, structures, and properties of several highly twisted alkenes are comprehensively explored. A facile and practical synthetic approach to target molecules is developed. The twist angles and lengths of the central C = C bonds in these molecules are 36-58° and 1.40-1.43 Å, respectively, and confirmed by X-ray crystallography and DFT calculations. A quasi-planar molecular half with the π-extended substituents delivers a shallow rotational barrier (down to 2.35 kcal/mol), indicating that the rotation of the C = C bond is as facile as that of the aryl-aryl bond in 2-flourobiphenyl. Other versatile and unique properties of the studied compounds include a broad photoabsorption range (from 250 up to 1100 nm), a reduced HOMO-LUMO gap (1.26-1.68 eV), and a small singlet-triplet energy gap (3.65-5.68 kcal/mol).

Highly Distorted Multiple Helicenes: Syntheses, Structural Analyses, and Properties.

A series of hexapole helicenes (HHs) and nonuple helicenes (NHs) were prepared from 1,3,5-tris[2-(arylethynyl)phenyl]benzene through two steps, namely, iodocyclization and subsequent palladium-catalyzed annulation with ortho-bromoaryl carboxylic acids. The crucial advantages of this synthetic method are the facile introduction of substituents, high regioselectivity, and efficient backbone extension. Three-dimensional structures of three C1-symmetric HHs and one C3-symmetric NH were elucidated using X-ray crystallography. Unlike most conventional multiple helicenes, the HHs and NHs investigated herein possess a unique structural feature where some double helical moieties share a terminal naphthalene unit. Chiral resolution of a HH and an NH was successfully achieved, and the enantiomerization barrier (ΔH‡) of the HH was experimentally determined to be 31.2 kcal/mol. A straightforward method for predicting the most stable diastereomer was developed based on density functional theory calculations and structural considerations. It was found that the relative potential energies (ΔHrs) of all diastereomers for two HHs and one NH can be obtained using minimal computational effort to analyze the types, helical configurations, numbers, and ΔH(MP-MM)s [= H(M,P/P,M) - H(M,M/P,P)] of the double helicenyl fragments.

Gold-Catalyzed Addition of ß-Oxo Enols at Tethered Alkynes via a Non-Conia-ene Pathway: Observation of a Formal 1,3-Hydroxymethylidene Migration.

With the relay process of Ag(I)/Au(I) catalysts, a one-pot synthesis of skeletally rearranged (1-hydroxymethylidene)indene derivatives from 2-alkynylbenzaldehydes and α-diazo esters is described. This cascade sequence involves Au(I)-catalyzed 5-endo-dig attack of highly enolizable aldehydes at the tethered alkynes, leading to carbocyclizations with a formal 1,3-hydroxymethylidene transfer. On the basis of density functional theory calculations, the mechanism likely involves formation of cyclopropylgold carbenes, followed by an appealing 1,2-cyclopropane migration.

Copper (I) Chloride-Catalyzed Photoredox Synthesis of Multifunctionalized Compounds at Room Temperature and Their Antifungal Activities.

A simple visible-light-induced CuCl-catalyzed synthesis was developed for highly functionalized carbon-centered compounds (α-alk/aryloxy-α-diaryl/alkylaryl-acetaldehydes/ketones) at room temperature using benzoquinone, alkyl/aryl alcohol, and alkyl/aryl terminal/internal alkynes. Late-stage functionalized compounds show good antifungal activities, especially against Candida krusei fungal strain, in in vitro experiments (the Broth microdilution method). Moreover, toxicity tests (zebrafish egg model experiments) indicated that these compounds had negligible cytotoxicity. The green chemistry metrics (E-factor value is 7.3) and eco-scale (eco-scale value is 58.8) evaluations show that the method is simple, mild, highly efficient, eco-friendly, and environmentally feasible.

Nitrosoarenes Implement Cascade Cyclization of 1-Allenyl-2-alkynylbenzenes through Diradical Mechanism.

This work reports cascade cyclization between 1-allenyl-2-alkynylbenzenes and nitrosoarenes. When these two components reacted alone under N2, N,O-functionalized indane-fused isoxazolidines 3 were obtained selectively. DFT calculations verify that this reaction sequence involves unprecedented nitrone/alkyne cycloadditions, followed by diradical rearrangement.

Stabilization of a high-spin three-coordinate Fe(iii) imidyl complex by radical delocalization.

High-spin, late transition metal imido complexes have attracted significant interest due to their group transfer reactivity and catalytic C-H activation of organic substrates. Reaction of a new two-coordinate iron complex, Fe{N( t Bu)Dipp}2 (1, Dipp = 2,6-diisopropylphenyl), with mesitylazide (MesN3) afforded a three-coordinate Fe-imidyl complex, Fe{N( t Bu)Dipp}2([double bond, length as m-dash]NMes) (2). X-ray crystallographic characterization of single crystals of 2 showed a long Fe-N distance of 1.761(1) Å. Combined magnetic and spectroscopic (Mössbauer and X-ray absorption near edge structure spectroscopy, XANES) characterization of 2 suggests that it has an S = 2 ground state comprising an S = 5/2 Fe(iii) center antiferromagnetically coupled to an S = 1/2 imidyl ligand. Reaction of 1 and 1-azidoadamantane (AdN3) generated a putative, transient Fe{N( t Bu)Dipp}2([double bond, length as m-dash]NAd) (3') complex that yielded an intramolecular C-H amination product, Fe{N( t Bu)Dipp}{κ2-N,N'-_N(CMe2CH2̲NHAd)Dipp} (3). Quantum mechanical calculations further confirmed the spectroscopic assignment of 2 and 3', as well as the differences in their stability and reactivity. Importantly, imidyl radical delocalization onto the mesityl ring significantly increased the stability of 2 and reduced its reactivity toward potential hydrogen atom transfer (HAT) reagents. In contrast, quantum mechanical calculations of 3' revealed that the radical was solely localized on the imidyl N, leading to a high reactivity toward the proximal C-H bond of the N( t Bu)Dipp- ligand.

Reactions of thioalkynes with diarylketenes via [3+2]-annulation versus benzannulation using Au and P(C6F5)3 catalysts.

Two catalytic annulations of non-symmetric diarylketenes with thioalkynes are described using gold and phosphine catalysts respectively. We employed α-aryldiazo ketones to generate gold-π-ketenes, ultimately yielding azulen-1-one derivatives. With the same reactants, we utilized P(C6F5)3 to increase the yields of 1-naphthols, notably with a complete regioselectivity.

Gold-Catalyzed Rearrangement of α-Carbonyl Cyclopropanes to Form 3-(Cyclopenta-1,3-dien-1-ylmethyl)oxindoles via a Postulated 1,5-Enolate Shift.

Gold-catalyzed stereoselective synthesis of spirocyclopropyl oxindoles from diazooxindoles and 1,2,4-substituted dienes is described. The aim of this work is to report a novel rearrangement of these spirocyclopropyl oxindoles with a gold catalyst to yield 3-(cyclopenta-1,3-dien-1-ylmethyl)oxindoles. Our experimental data exclude a reversible process in the gold-catalyzed cyclopropanation. With DFT calculations, we postulate a rearrangement mechanism involving the formation of complex pairs of gold enolates and 1-methylen-2,3,4-cyclopentadienyl cations, leading to a 1,5-enolate shift.

Highly Substituted Acephenanthrylenes and Their π-Extended Derivatives: Syntheses, Structural Analyses, and Properties.

This investigation demonstrates that a series of (highly) substituted acephenanthrylenes (APs) 2, benzo[l]acephenanthrylene 3, and dicyclopenta[cd,mn]pyrene 4 are easily prepared by palladium-catalyzed cycloaromatization of 2,3-diethynylbiphenyls 1. The first nonpyrolysis synthesis of 4 by two-fold cycloaromatization was achieved in a high yield. This synthetic protocol has two crucial advantages: facile introduction of various substituents and efficient extension of the AP backbone.

Examination of the Brønsted-Evans-Polanyi relationship for the hydrogen evolution reaction on transition metals based on constant electrode potential density functional theory.

In the search for efficient and inexpensive electrocatalysts for the hydrogen evolution reaction (HER), the hydrogen binding energy is often used as a descriptor to represent the catalytic activity. The success of this approach relies on the Brønsted-Evans-Polanyi (BEP) relationship. In this study, we used constant electrode potential density functional theory calculations to examine this relationship. Eight fcc metals with a low hydrogen adsorption concentration of 1/9 were used as the model systems. We found that the HER kinetic barriers are indeed correlated to the . Both the s of the hollow site and less favourable top site correlate to the kinetic barriers; however, the correlation is better for the latter. This behaviour leads to a set of equations for estimating the HER kinetic barriers with improved accuracy that can be used to predict the HER performance of the materials with a low hydrogen adsorption concentration. This work demonstrates the importance of calculating the of a suitable adsorption site to establish good BEP relationships.

Diindeno[2,1-b:2',1'-h]biphenylenes: Syntheses, Structural Analyses, and Properties.

A series of diindeno[2,1-b:2',1'-h]biphenylenes with open-shell singlet ground states and interesting properties were prepared. The studied compounds consist of p-quinodimethane moieties, which suffer from geometric perturbation with bond angles of around 90°. The substituent effects on structural parameters, local aromaticity, and properties were systematically explored.

Gold Catalysts Can Generate Nitrone Intermediates from a Nitrosoarene/Alkene Mixture, Enabling Two Distinct Catalytic Reactions: A Nitroso-Activated Cycloheptatriene/Benzylidene Rearrangement.

Gold-catalyzed reactions of cycloheptatrienes with nitrosoarenes yield nitrone derivatives efficiently. This reaction sequence enables us to develop gold-catalyzed aerobic oxidations of cycloheptatrienes to afford benzaldehyde derivatives using CuCl and nitrosoarenes as co-catalysts (10-30 mol %). Our density functional theory calculations support a novel nitroso-activated rearrangement, tropylium → benzylidene. With the same nitrosoarenes, we developed their gold-catalyzed [2 + 2 + 1]-annulations between nitrosobenzene and two enol ethers to yield 5-alkoxyisoxazolidines using 1,4-cyclohexadienes as hydrogen donors.

Electrokinetic and in situ spectroscopic investigations of CO electrochemical reduction on copper.

Rigorous electrokinetic results are key to understanding the reaction mechanisms in the electrochemical CO reduction reaction (CORR), however, most reported results are compromised by the CO mass transport limitation. In this work, we determined mass transport-free CORR kinetics by employing a gas-diffusion type electrode and identified dependence of catalyst surface speciation on the electrolyte pH using in-situ surface enhanced vibrational spectroscopies. Based on the measured Tafel slopes and reaction orders, we demonstrate that the formation rates of C2+ products are most likely limited by the dimerization of CO adsorbate. CH4 production is limited by the CO hydrogenation step via a proton coupled electron transfer and a chemical hydrogenation step of CO by adsorbed hydrogen atom in weakly (7 < pH < 11) and strongly (pH > 11) alkaline electrolytes, respectively. Further, CH4 and C2+ products are likely formed on distinct types of active sites.