Controlled Generation of 9‐Boratriptycene by Lewis Adduct Dissociation: Accessing a Non‐Planar Triarylborane

A highly bent triarylborane, 9‐boratriptycene, was generated in solution by selective protodeboronation of the corresponding tetra‐aryl boron ate complex with the strong Brønsted acid HNTf₂. The iptycene core confers enhanced Lewis acidity to 9‐boratriptycene, making it unique in terms of structure and reactivity. We studied the stereoelectronic properties of 9‐boratriptycene by quantifying its association with small N‐ and O‐centered Lewis bases, as well as with sterically hindered phosphines. The resultant Lewis adducts exhibited unique structural, spectroscopic, and photophysical properties. Beyond the high pyramidalization of the 9‐boratriptycene scaffold and its low reorganization energy upon Lewis base coordination, quantum chemical calculations revealed that the absence of π donation from the triptycene aryl rings to the boron vacant p_z orbital is one of the main reasons for its high Lewis acidity.     

Catalytic Double Carbon–Boron Bond Formation for the Synthesis of Cyclic Diarylborinic Acids as Versatile Building Blocks for π‐Extended Heteroarenes

The first catalytic synthesis of cyclic diarylborinic acids is developed using a dihydroaminoborane reagent as the boron source. Unlike previously reported methods that use organolithium reagents, this method allows the easy synthesis of cyclic diarylborinic acids bearing a range of functionalities including CN, CO₂Et, CONEt₂ and NMeCO₂^t Bu. Furthermore, these cyclic diarylborinic acids provide rapid access to skeletal diversity, in particular they enable the synthesis of six‐ to nine‐membered π‐extended heteroarenes through simple cross‐coupling reactions, which are important synthetic targets in both advanced materials and pharmaceuticals.     

Intramolecular Aminocyanation of Alkenes by N?CN Bond Cleavage

A metal‐free, Lewis acid promoted intramolecular aminocyanation of alkenes was developed. B(C₆F₅)₃ activates N‐sulfonyl cyanamides, thus leading to a formal cleavage of the N CN bonds in conjunction with vicinal addition of sulfonamide and nitrile groups across an alkene. This method enables atom‐economical access to indolines and tetrahydroquinolines in excellent yields, and provides a complementary strategy for regioselective alkene difunctionalizations with sulfonamide and nitrile groups. Labeling experiments with ¹³C suggest a fully intramolecular cyclization pattern due to the lack of label scrambling in double crossover experiments. Catalysis with Lewis acid is realized and the reaction can be conducted under air.     

Enantioselective Addition Reaction of Azlactones with Styrene Derivatives Catalyzed by Strong Chiral Brønsted Acids

An enantioselective intermolecular addition reaction of azlactones, as carbon nucleophiles, with styrene derivatives, as simple olefins, was demonstrated using a newly developed chiral Brønsted acid catalyst, namely, F₁₀BINOL‐derived N‐triflyl phosphoramide. Addition products having vicinal tetrasubstituted carbon centers, one of which is an all‐carbon quaternary stereogenic center, were formed in good yields with moderate to high stereoselectivities. Extremely high acidity of the new chiral Brønsted acid was confirmed by its calculated pK_a value based on DFT studies and is the key to accomplishing not only high catalytic activity but also efficient stereocontrol in the intermolecular addition.     

Selective [3+1] Fragmentations of P4 by “P” Transfer from a Lewis Acid Stabilized [RP4]− Butterfly Anion

Two [3+1] fragmentations of the Lewis acid stabilized bicyclo[1.1.0]tetraphosphabutanide Li[Mes*P₄⋅ BPh₃] (Mes*=2,4,6‐tBu₃C₆H₂) are reported. The reactions proceed by extrusion of a P₁ fragment, induced by either an imidazolium salt or phenylisocyanate, with release of the transient triphosphirene Mes*P₃, which was isolated as a dimer and trapped by 1,3‐cyclohexadiene as a Diels–Alder adduct. DFT quantum chemical computations were used to delineate the reaction mechanisms. These unprecedented pathways grant access to both P₁‐ and P₃‐containing organophosphorus compounds in two simple steps from white phosphorus.     

Alternating Radical Stabilities: A Convergent Route to Terminal and Internal Boronates

Pinacolato boronates (Bpin) with an empty p‐orbital on boron stabilize an adjacent carbon radical, in contrast to diethanolamino boronates [B(DEA)] where the boron is sp³‐hybridized. By alternately placing a pinacol or diethanolamine moiety on the boron atom, thus stabilizing or not stabilizing the corresponding adjacent radical, it is possible to control the behavior of α‐boronyl xanthates and construct a large variety of terminal or internal boronates in a modular fashion. The remarkable tolerance of polar groups and the ability to introduce quaternary centers are particularly noteworthy features of this process.     

Borane‐Stabilized Isomeric Dimers of the Phosphaethynolate Anion

The reactions of the phosphaethynolate anion ([PCO]⁻) with a range of boranes were explored. BPh₃ and [PCO]⁻ form a dimeric anion featuring P−B bonds and is prone to dissociation at room temperature. The more Lewis acidic borane B(C₆F₅)₃ yields a less symmetric dimer of [PCO]⁻ with P−B and P−O bonds. Less sterically demanding HB(C₆F₅)₂ and H₂B(C₆F₅) boranes form a third isomer with [PCO]⁻ featuring both boranes bound to the same phosphorus atom. Despite the unexpected thermodynamic preference for P‐coordination, computational data illustrate that electronic and steric features impact the binding modes of the resulting dianionic dimers.     

A New Mode of Chemical Reactivity for Metal‐Free Hydrogen Activation by Lewis Acidic Boranes

We herein explore whether tris(aryl)borane Lewis acids are capable of cleaving H₂ outside of the usual Lewis acid/base chemistry described by the concept of frustrated Lewis pairs (FLPs). Instead of a Lewis base we use a chemical reductant to generate stable radical anions of two highly hindered boranes: tris(3,5‐dinitromesityl)borane and tris(mesityl)borane. NMR spectroscopic characterization reveals that the corresponding borane radical anions activate (cleave) dihydrogen, whilst EPR spectroscopic characterization, supported by computational analysis, reveals the intermediates along the hydrogen activation pathway. This radical‐based, redox pathway involves the homolytic cleavage of H₂, in contrast to conventional models of FLP chemistry, which invoke a heterolytic cleavage pathway. This represents a new mode of chemical reactivity for hydrogen activation by borane Lewis acids.     

Scandium‐Catalyzed Self‐Assisted Polar Co‐monomer Enchainment in Ethylene Polymerization

Direct coordinative copolymerization of ethylene with functionalized co‐monomers is a long‐sought‐after approach to introducing polyolefin functionality. However, functional‐group Lewis basicity typically depresses catalytic activity and co‐monomer incorporation. Finding alternatives to intensively studied group 4 d⁰ and late‐transition‐metal catalysts is crucial to addressing this long‐standing challenge. Shown herein is that mono‐ and binuclear organoscandium complexes with a borate cocatalyst are active for ethylene + amino olefin [AO; H₂C=CH(CH₂)_nNR₂] copolymerizations in the absence of a Lewis‐acidic masking reagent. Both activity (up to 4.2×10² kg mol⁻¹⋅h^−1> atm^−1>) and AO incorporation (up to 12 % at 0.2 m [AO]) are appreciable. Linker‐length‐dependent (n) AO incorporation and mechanistic probes support an unusual functional‐group‐assisted enchainment mechanism. Furthermore, the binuclear catalysts exhibit enhanced AO tolerance and enhanced long chain AO incorporation.     

Boron(III) Carbazosubphthalocyanines: Core‐Expanded Antiaromatic Boron(III) Subphthalocyanine Analogues

Condensation of 1,8‐diamino‐3,6‐dichlorocarbazole with a series of disubstituted 1,3‐diiminoisoindolines, followed by treatment with BF₃?OEt₂ led to the formation of the corresponding core‐expanded boron(III) subphthalocyanine analogues. These air‐stable π‐conjugated boron(III) carbazosubphthalocyanines possess two boron‐containing seven‐membered‐ring units and a 16 π‐electron skeleton, and represent the first examples of antiaromatic boron(III) subphthalocyanine analogues as supported by spectroscopic and theoretical studies. The molecular structure of one of these compounds was unambiguously determined by single‐crystal X‐ray diffraction analysis. In contrast to typical boron(III) subphthalocyanines, which adopt a cone‐shaped structure, the π skeleton of this compound is almost planar.     

Controlled Generation of 9-Boratriptycene by Lewis Adduct Dissociation: Accessing a Non-Planar Triarylborane

A highly bent triarylborane, 9-boratriptycene, was generated in solution by selective protodeboronation of the corresponding tetra-aryl boron ate complex with the strong Brønsted acid HNTf₂. The iptycene core confers enhanced Lewis acidity to 9-boratriptycene, making it unique in terms of structure and reactivity. We studied the stereoelectronic properties of 9-boratriptycene by quantifying its association with small N- and O-centered Lewis bases, as well as with sterically hindered phosphines. The resultant Lewis adducts exhibited unique structural, spectroscopic, and photophysical properties. Beyond the high pyramidalization of the 9-boratriptycene scaffold and its low reorganization energy upon Lewis base coordination, quantum chemical calculations revealed that the absence of π donation from the triptycene aryl rings to the boron vacant p_z orbital is one of the main reasons for its high Lewis acidity.     

Cationic Gold(III) Alkyl Complexes: Generation,Trapping, and Insertion of Norbornene

Migratory insertion of alkenes into gold–carbon bonds, a fundamental yet unprecedented organometallic transformation, has been investigated from a discrete (P,C) cyclometalated gold(III) dimethyl complex. Methide abstraction by B(C₆F₅)₃ is shown to generate a highly reactive cationic Au^III complex that evolves spontaneously by C₆F₅ transfer from boron. In the presence of norbornene, migratory insertion into the Au C bond proceeds readily. The resulting norbornyl complex is efficiently trapped with pyridines or chloride to give stable four‐coordinate adducts.     

The Arene‐Stabilized η5‐Pentamethylcyclopentadienyl Arsenic Dication [(η5‐Cp*)As(toluene)]2+

Double chloride abstraction of Cp*AsCl₂ gives the dicationic arsenic species [(η⁵‐Cp*)As(tol)][B(C₆F₅)₄]₂ ( 2 ) (tol=toluene). This species is shown to exhibit Lewis super acidity by the Gutmann–Beckett test and by fluoride abstraction from [NBu₄][SbF₆]. Species 2 participates in the FLP activation of THF affording [(η²‐Cp*)AsO(CH₂)₄(THF)][B(C₆F₅)₄]₂ ( 5 ). The reaction of 2 with PMe₃ or dppe generates [(Me₃P)₂As][B(C₆F₅)₄] ( 6 ) and [(σ‐Cp*)PMe₃][B(C₆F₅)₄] ( 7 ), or [(dppe)As][B(C₆F₅)₄] ( 8 ) and [(dppe)(σ‐Cp*)₂][B(C₆F₅)₄]₂ ( 9 ), respectively, through a facile cleavage of C?As bonds, thus showcasing unusual reactivity of this unique As‐containing compound.     

Allyl‐Palladium‐Catalyzed α,β‐Dehydrogenation of Carboxylic Acids via Enediolates

A highly practical and step‐economic α,β‐dehydrogenation of carboxylic acids via enediolates is reported through the use of allyl‐palladium catalysis. Dianions underwent smooth dehydrogenation when generated using Zn(TMP)₂⋅2 LiCl as a base in the presence of excess ZnCl₂, thus avoiding the typical decarboxylation pathway of these substrates. Direct access to 2‐enoic acids allows derivatization by numerous approaches.     

Room‐Temperature Activation of H2 by a Surface Frustrated Lewis Pair

Surface frustrated Lewis pairs (SFLPs) have been implicated in the gas‐phase heterogeneous (photo)catalytic hydrogenation of CO₂ to CO and CH₃OH by In₂O_3?x(OH)_y. A key step in the reaction pathway is envisioned to be the heterolysis of H₂ on a proximal Lewis acid–Lewis base pair, the SFLP, the chemistry of which is described as In???In‐OH + H₂ → In‐OH₂⁺???In‐H^?. The product of the heterolysis, thought to be a protonated hydroxide Lewis base In‐OH₂⁺ and a hydride coordinated Lewis acid In‐H^?, can react with CO₂ to form either CO or CH₃OH. While the experimental and theoretical evidence is compelling for heterolysis of H₂ on the SFLP, all conclusions derive from indirect proof, and direct observation remains lacking. Unexpectedly, we have discovered rhombohedral In₂O_3?x(OH)_y can enable dissociation of H₂ at room temperature, which allows its direct observation by several analytical techniques. The collected analytical results lean towards the heterolysis rather than the homolysis reaction pathway.     

Stabilized Carbenium Ions as Latent,Z‐type Ligands

Controlling the reactivity of transition metals using secondary, σ‐accepting ligands is an active area of investigation that is impacting molecular catalysis. Herein we describe the phosphine gold complexes [(o‐Ph₂P(C₆H₄)Acr)AuCl]⁺ ([ 3 ]⁺; Acr=9‐N‐methylacridinium) and [(o‐Ph₂P(C₆H₄)Xan)AuCl]⁺ ([ 4 ]⁺; Xan=9‐xanthylium) where the electrophilic carbenium moiety is juxtaposed with the metal atom. While only weak interactions occur between the gold atom and the carbenium moiety of these complexes, the more Lewis acidic complex [ 4 ]⁺ readily reacts with chloride to afford a trivalent phosphine gold dichloride derivative ( 7 ) in which the metal atom is covalently bound to the former carbocationic center. This anion‐induced Au^I/Au^III oxidation is accompanied by a conversion of the Lewis acidic carbocationic center in [ 4 ]⁺ into an X‐type ligand in 7 . We conclude that the carbenium moiety of this complex acts as a latent Z‐type ligand poised to increase the Lewis acidity of the gold center, a notion supported by the carbophilic reactivity of these complexes.     

Stabilized Carbenium Ions as Latent,Z‐type Ligands

Controlling the reactivity of transition metals using secondary, σ‐accepting ligands is an active area of investigation that is impacting molecular catalysis. Herein we describe the phosphine gold complexes [(o‐Ph₂P(C₆H₄)Acr)AuCl]⁺ ([ 3 ]⁺; Acr=9‐N‐methylacridinium) and [(o‐Ph₂P(C₆H₄)Xan)AuCl]⁺ ([ 4 ]⁺; Xan=9‐xanthylium) where the electrophilic carbenium moiety is juxtaposed with the metal atom. While only weak interactions occur between the gold atom and the carbenium moiety of these complexes, the more Lewis acidic complex [ 4 ]⁺ readily reacts with chloride to afford a trivalent phosphine gold dichloride derivative ( 7 ) in which the metal atom is covalently bound to the former carbocationic center. This anion‐induced Au^I/Au^III oxidation is accompanied by a conversion of the Lewis acidic carbocationic center in [ 4 ]⁺ into an X‐type ligand in 7 . We conclude that the carbenium moiety of this complex acts as a latent Z‐type ligand poised to increase the Lewis acidity of the gold center, a notion supported by the carbophilic reactivity of these complexes.     

Diferrocenophosphaborin: A Planar‐Chiral,Redox‐Active and Anion‐Responsive Ambiphilic Ligand

A new class of Janus‐like ambiphilic ligands is introduced. The rigid diferrocene backbone in heterocycles 4‐SnP and 4‐BP creates an unprecedented chiral environment as demonstrated by multinuclear NMR and single‐crystal X‐ray studies. In addition, the ligands are redox‐responsive and the Lewis acidic borane moiety in 4‐BP can be exploited to further tune the properties: a clear decrease in the CO stretching frequency of a Vaska‐type Rh^I complex 5‐BP is observed upon addition of fluoride ions. Thus, the Lewis acid and Lewis base sites influence each other and their strength can be modulated by redox chemistry and anion binding.     

Elusive Silane–Alane Complex [Si?H⋅⋅⋅Al]: Isolation,Characterization, and Multifaceted Frustrated Lewis Pair Type Catalysis

The super acidity of the unsolvated Al(C₆F₅)₃ enabled isolation of the elusive silane–alane complex [Si H⋅⋅⋅Al], which was structurally characterized by spectroscopic and X‐ray diffraction methods. The Janus‐like nature of this adduct, coupled with strong silane activation, effects multifaceted frustrated‐Lewis‐pair‐type catalysis. When compared with the silane–borane system, the silane–alane system offers unique features or clear advantages in the four types of catalytic transformations examined in this study, including: ligand redistribution of tertiary silanes into secondary and quaternary silanes, polymerization of conjugated polar alkenes, hydrosilylation of unactivated alkenes, and hydrodefluorination of fluoroalkanes.     

A Lewis Base Catalysis Approach for the Photoredox Activation of Boronic Acids and Esters

We report herein the use of a dual catalytic system comprising a Lewis base catalyst such as quinuclidin‐3‐ol or 4‐dimethylaminopyridine and a photoredox catalyst to generate carbon radicals from either boronic acids or esters. This system enabled a wide range of alkyl boronic esters and aryl or alkyl boronic acids to react with electron‐deficient olefins via radical addition to efficiently form C−C coupled products in a redox‐neutral fashion. The Lewis base catalyst was shown to form a redox‐active complex with either the boronic esters or the trimeric form of the boronic acids (boroxines) in solution.