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CONTENTS 1. Introduction 4246 2. History of Borenium Ions: Often Considered, Seldom Confirmed 4247 2.1. Suspected Intermediates in B−N Protonation 4247 2.2. Hypothetical Isomers of Cl 3 B•NHMe 2 4247 2.3. The First Observable Borenium Salt 4247 2.4. Nucleophilic Substitution of X 3 B•NR 3 and Py•BF 2 X 4248 2.5. Aminoborenium Ions, Stabilization by n-Delocalization 4249 3. Recent Developments in the Generation of Observable Borenium Intermediates 4249 3.1. Electrophilic Activation by Protonation or by Lewis Acid Catalysis 4249 3.2. Halide Abstraction by a Halophile 4250 3.3. The Borinium−Borenium Interface: Gas-Phase Oxyborenium Ions 4251 3.4. Borenium Salt Generation by Hydride Abstraction 4251 3 . 4 . 1 . H y d r i d e A b s t r a c t i o n b y T r i s -(pentafluorophenyl)borane 4251 3.4.2. Hydride Abstracton by Trityl Salts 4252 3.4.3. Hydride-Bridged Borenium Salt Dimers 4252 3.5. Borenium Ion Generation by Nucleophilic Addition−Heterolysis 4253 4. Borenium Lewis Acidity vs Structure 4254 4.1. Experimental Evaluation of Lewis Acidity 4254 4.2. Computational Evaluation of Borenium Lewis Acidity 4255 5. Borenium Ions and Stereogenic Boron 4257 5.1. Racemization by Heterolysis 4257 5.2. Asymmetric Memory at Stereogenic Boron 4257 5.3. Chiral Salicylaldimine Boronate Complexes 4258 6. Enantioselective Catalysis and Chiral Borenium Ions 4259 6.1. The Dual Function of Oxazaborolidines in the CBS Reduction 4260 6.2. The Role of Borenium Species in Diels−Alder Catalysis 4261 6.3. Reactivity and Scope of Oxazaborolidine-Derived Diels−Alder Catalysts 4263 6.4. Miscellaneous Uses of Chiral Borenium Lewis Acid Catalysts 4265 7. Miscellaneous Applications of Borenium Lewis Acids 4266 7.1. B−O Activation 4266 7.2. Lewis Acidity and π-Conjugated Borenium Analogues 4267 7.3. π-Conjugated Borenium Analogues as Selective Anion Sensors 4268 7.4. Tricoordinate Boron in Structures Containing Metal Cations 4269 8. Borenium Reagents for C−B Bond Formation 4269 8.1. Borenium Ion Equivalents 4269 8.2. Do Borenium Ions Participate in Hydroboration Chemistry? 4270 8.3. Borenium Equivalents in Electrophilic Aromatic Borylation 4271 8.3.1. Intramolecular Borylation 4271 8.3.2. Intermolecular Borylation 4272 8.3.3. Recent Developments in Muetterties Borylation (BX3 plus Proton Scavenger) 4275 9. Extension of Borenium Chemistry to Neighboring Fields and Unusual Environments 4276 9.1. N-Heterocyclic Carbenes as Stabilizing Ligands for Borenium Salts 4276 9.2. Miscellaneous Related Topics Involving BH Species 4277 10. Summary 4278 Author Information 4279 Corresponding Author 4279 Notes 4279 Biographies 4279 Acknowledgments 4279 References 4279

Flexible organic materials possessing useful electrical properties, such as ferroelectricity, are of crucial importance in the engineering of electronic devices. Up until now, however, only ferroelectric polymers have intrinsically met this flexibility requirement, leaving small-molecule organic ferroelectrics with room for improvement. Since both flexibility and ferroelectricity are rare properties on their own, combining them in one crystalline organic material is challenging. Herein, we report that trisubstituted haloimidazoles not only display ferroelectricity and piezoelectricity—the properties that originate from their non-centrosymmetric crystal lattice—but also lend their crystalline mechanical properties to fine-tuning in a controllable manner by disrupting the weak halogen bonds between the molecules. This element of control makes it possible to deliver another unique and highly desirable property, namely crystal flexibility. Moreover, the electrical properties are maintained in the flexible crystals.

Treatment of alkenes such as 3-hexene, 3-octene, and 1-cyclohexyl-1-butene with the N-heterocyclic carbene-derived borane 2 and catalytic HNTf2 effects hydroboration at room temperature. With 3-hexene, surprisingly facile migration of the boron atom from C3 of the hexyl group to C2 was observed over a time scale of minutes to hours. Oxidative workup gave a mixture of alcohols containing 2-hexanol as the major product. A similar preference for the C(2) alcohol was observed after oxidative workup of the 3-octene, and 1-cyclohexyl-1-butene hydroborations. NHC-borenium cations (or functional equivalents) are postulated as the species that accomplish the hydroborations, and the C(2) selective migrations are attributed to the 4-center inter-conversion of borenium cations with cationic NHC-borane olefin π-complexes.

The first examples of borylation under conditions of borenium ion generation from hydrogen-bridged boron cations are described. The observable H-bridged cations are generated by hydride abstraction from N,N-dimethylamine boranes Ar(CH2)nNMe2BH3 using Ph3C+ (C6F5)4B− (TrTPFPB) as the hydride acceptor. In the presence of excess TrTPFPB, the hydrogen-bridged cations undergo internal borylation to afford cyclic amine borane derivatives with n = 1-3. The products are formed as the corresponding cyclic borenium ions according to reductive quenching experiments and 11B and 1H NMR spectroscopy in the case with Ar = C6H5 and n = 1. The same cyclic borenium cation is also formed from the substrate with Ar = o-C6H4SiMe3 via desilylation, but the analogous system with Ar = o-C6H4CMe3 affords a unique cyclization product that retains the tert-butyl substituent. An ortho-deuterated substrate undergoes cyclization with a product-determining isotope effect of kH/kD 2.8. Potential cationic intermediates have been evaluated using B3LYP/6-31G* methods. The computations indicate that internal borylation from 14a occurs via a C–H insertion transition state that is accessible from either the borenium π complex or from a Wheland intermediate having nearly identical energy. The Ar = o-C6H4SiMe3 example strongly favors formation of the Wheland intermediate, and desilylation occurs via internal SiMe3 migration from carbon to one of the hydrides attached to boron.

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Organic rechargeable batteries, composed of redox-active molecules, are emerging as candidates for the next generation of energy storage materials because of their large specific capacities, cost effectiveness, and the abundance of organic precursors, when compared with conventional lithium-ion batteries. Although redox-active molecules often display multiple redox states, precise control of a molecule's redox potential, leading to a single output voltage in a battery, remains a fundamental challenge in this popular field of research. By combining macrocyclic chemistry with density functional theory calculations (DFT), we have identified a structural motif that more effectively delocalizes electrons during lithiation events in battery operations-namely, through-space electron delocalization in triangular macrocyclic molecules that exhibit a single well-defined voltage profile-compared to the discrete multiple voltage plateaus observed for a homologous macrocyclic dimer and an acyclic derivative of pyromellitic diimide (PMDI). The triangular macrocycle, incorporating three PMDI units in close proximity to one another, exhibits a single output voltage at 2.33 V, compared with two peaks at (i) 2.2 and 1.95-1.60 V for reduction and (ii) 1.60-1.95 and 2.37 V for oxidation of the acyclic PMDI derivative. By investigating the two cyclic derivatives with different conformational dispositions of their PMDI units and the acyclic PMDI derivative, we identified noticeable changes in interactions between the PMDI units in the two cyclic derivatives under reducing conditions, as determined by differential pulse voltammetry, solution-state spectroelectrochemistry, and variable-temperature UV-Vis spectra. The numbers and relative geometries of the PMDI units are found to alter the voltage profile of the active materials significantly during galvanostatic measurements, resulting in a desirable single plateau for the triangular macrocycle. The present investigation reveals that understanding and controlling the relative conformational dispositions of redox-active units in macrocycles are key to achieving high energy density and long cycle-life electrodes for organic rechargeable batteries.

Highly electrophilic boron cations derived from hindered amine borane complexes have been shown to undergo intramolecular aliphatic C–H borylation.