Coordination Of Lewis Acid Research Articles

Lewis-Acid-Promoted Visible-Light-Mediated C(sp3)-H Bond Functionalization of Arylvinylpyridines via Diradical Hydrogen Atom Transfer.

A visible-light-induced intramolecular diradical-mediated hydrogen atom transfer (DHAT) of primary, secondary, and tertiary C(sp3)-H bonds and subsequent cyclization is described. This transformation is enabled by triplet energy transfer upon Lewis acid coordination to alkyl-substituted arylvinylpyridines and gives access to a variety of benzocyclobutenes (>40 examples, 32-96% yield). Notably, tri- and tetrasubstituted olefins with tertiary C(sp3)-H bonds effectively delivered sterically hindered products with adjacent all-carbon quaternary centers. Mechanistic evidence and density functional theory (DFT) calculations suggest that Lewis acid coordination was crucial for the success by modulating the reactivity of the diradical intermediates to unlock a challenging carbon-to-carbon DHAT and subsequent cyclization with a rather low barrier, which allows the functionalization of benzylic C(sp3)-H bonds to construct otherwise inaccessible benzocyclobutenes.

Catalytic Intramolecular Ketone Haloacylation Enabled Stereoselective Heterolytic Cleavage of Cyclopropyl Ketones with Enhanced Reactivity and Regioselectivity beyond Electronics.

By integration of oxocarbenium activation and Lewis acid coordination activation via conformational proximity-driven, Pd(II)- or Cu(I)-catalyzed intramolecular ketone haloacylation, regio- and stereoselective heterolytic ring-opening 1,5-haloacylation of cyclopropyl ketones, including those with weak single alkyl donors, has been developed for the synthesis of valuable α-quaternary halo-γ-butenolides. The vicinal carboxylic acid and ketone acceptors are no longer just spectator activators. Further, this reaction delivers a constant regioselectivity regardless of the electronic nature of substituents, even the malonate.

Combined Nucleophilic and Electrophilic Functionalization to Optimize Blue Phosphorescence in Cyclometalated Platinum Complexes.

Ligand-based functionalization strategies have emerged as powerful approaches to tune and optimize blue phosphorescence, which can involve nucleophilic addition to coordinated ligands or electrophilic functionalization via the coordination of exogenous Lewis acids. Whereas both have been used separately to enhance the photophysical properties of organometallic compounds with high-energy triplet states, in this work, we show that these two strategies can be used together on the same platform. Isocyanide-supported cyclometalated platinum compounds undergo nucleophilic addition with diethylamine to form a strong σ-donor acyclic diaminocarbene-supporting ligand. In a subsequent step, a cyanide ancillary ligand is converted into a more strongly π-acidic isocyanoborate via the coordination of a borane Lewis acid. Importantly, both of these ligand-based functionalization steps improve the quantum yields and lifetimes of the blue-phosphorescent complexes. This synergy results in complexes with photoluminescence quantum yields up to 0.40 for deep blue and 0.75 for sky blue regions and PL lifetimes on the order of 10-5 s.

Bond-alternated and bond-equalized hexazine derivatives.

Planar cyclic conjugated molecules satisfying the Hückel rule are generally classified as aromatics and π delocalization is the key feature of aromatic compounds. It was shown that the π system of benzene prefers bond-alternation and that the delocalization observed is a consequence of bond-equalization, which is a σ effect. For systems wherein the π bonds are strong, such as those between N atoms, the π-distortivity may outweigh the σ preference for bond-equalization. Thus, one anticipates a bond-alternated structure for N6; however, neither the bond-equalized structure (D6h) nor the bond-alternated one (D3h) is a minimum as evident from the previous literature; calculations have shown that cyclic N6 is non-planar. Herein we show that a Lewis acid coordination strategy can be employed to stabilize the planar structure of N6. We show that the structure can be bond-alternated or bond-equalized depending on the strength of the Lewis acid. Kinetic stability with respect to concerted decomposition to three N-N triple bonded systems was assessed, and a few bond-equalized N6 systems were found to be potential candidates for synthesis.

Enhanced carboxylation of furoic salt with CO2 by ZnCl2 coordination for efficient production of 2,5-furandicarboxylic acid.

C-H carboxylation of furoic acid (FA) with CO2 is an atom-efficient strategy to produce 2,5-furandicarboxylic acid (2,5-FDCA) from lignocellulose. The existing carbonate-promoted CO2 carboxylation processes rely on the use of large amounts of expensive Cs2CO3 as a deprotonating reagent and molten salt. Substitution of Cs with other cheap and abundant alkali ions (such as K and Na) can reduce the use of Cs, but it faces the problem of a low yield of 2,5-FDCA. This study found that the addition of catalytic amounts of ZnCl2 as a Lewis acid can increase the yield of 2,5-FDCA in the CO2 carboxylation reaction of Na/K-FA in a molten salt reaction system. 1H NMR analysis and DFT calculations confirmed that ZnCl2 coordinates with the furan ring through electron transfer from the conjugated furan ring to Zn2+, thereby activating the H at the C5 position of Na/K-FA. This coordination lengthened the C5-H bond and lowered its heterolytic dissociation energy, making it more susceptible to being deprotonated by CO32- and subsequently carboxylated by CO2. The developed Lewis acid coordination strategy provides a new idea for the efficient construction of C-C bonds between CO2 and aromatics through carbonate-promoted C-H carboxylation.

An Investigation of Allyl-Substituted Bis(Diphosphine) Iron Complexes: Towards Precursors for Cooperative CO2 Activation.

In developing homogenous catalysts capable of CO2 activation, interaction with a metal center is often imperative. This work provides primary efforts towards the cooperative activation of CO2 using a Lewis acidic secondary coordination sphere (SCS) and iron via a paired theoretical/experimental approach. Specifically, this study reports efforts towards [Fe(diphosphine)2 (N2 )] as a CO2 -coordinated synthon where diphosphine=1,2-bis(di(3-cyclohexylboranyl)propylphosphino)ethane) (P2 BCy 4 ) or its precursor, 1,2-bis(diallylphosphino)ethane (tape). Initial efforts toward the {Fe(0)-N2 } complex were focused on deprotonation reactions of [Fe(diphosphine)2 (H)(NCCH3 )]+ and reduction of [Fe(tape)2 Cl2 ]. In the latter case, a mixture of intramolecularly π-bonded alkene and associated metallacyclic Fe(II)-H species were produced - heating this mixture provided the hydride as the major product. Notably, the interconversion of this pair counters that of related intermolecular reactions between [Fe(depe)2 ] (depe=1,2-bis(diethylphosphino)ethane) and ethylene, where hydride formation occurs subsequent to π-coordination; this has been probed by theoretical calculations. Finally, reactivity of the metallacyclic {Fe(II)-H} complex with CO2 was probed, resulting in a pair of isomeric ferra(II)lactones.

Acceleration of Near-IR Emission through Efficient Surface Passivation in Cd3P2 Quantum Dots.

Fast near-IR (NIR) emitters are highly valuable in telecommunications and biological imaging. The most established NIR emitters are epitaxially grown InxGa1-xAs quantum dots (QDs), but epitaxial growth has several disadvantages. Colloidal synthesis is a viable alternative that produces a few NIR-emitting materials, but they suffer from long photoluminescence (PL) times. These long PL times are intrinsic in some NIR materials (PbS, PbSe) but are attributed to emission from bright trapped carrier states in others. We show that Cd3P2 QDs possess substantial trap emission with radiative times >101 ns. Surface passivation through shell growth or coordination of Lewis acids is shown to accelerate the NIR emission from Cd3P2 QDs by decreasing the amount of trap emission. This finding brings us one step closer to the application of colloidally synthesized QDs as quantum emitters.

Synthesis, crystal structure, and Hirshfeld surface analysis of 3-ferrocenyl-1-(pyridin-2-yl)-1H-pyrazol-5-amine.

A key step towards utilizing polynuclear metal-based systems in magnetic device applications involves the careful design of ligands. This strategic planning aims to produce metal assemblies that exhibit some kind of 'switch' mechanism. Towards this end, a ligand that incorporates a redox-active functional group (ferrocene) is reported. This communication presents the multi-step synthesis, characterization (1H and 13C NMR), and structural analysis (single-crystal X-ray diffraction and Hirshfeld surface analysis) of 3-ferrocenyl-1-(pyridin-2-yl)-1H-pyrazol-5-amine, [Fe(C5H5)(C13H11N4)]. Supra-molecular features, including π-π stacking and hydrogen bonding are qu-anti-fied, while a database search reveals the unique combination of mol-ecular moieties, which offer future opportunities for studies to involve simultaneous Lewis acid and base coordin-ation.

Catalytic Asymmetric Ring-Opening Reactions of Unstrained Heterocycles Using Cobalt Vinylidenes.

Cobalt catalysts promote highly enantioselective ring-opening reactions of 2,5-dihydrofurans using vinylidenes. The products are acyclic organozinc compounds that can be functionalized with an electrophile. The proposed mechanism involves the generation of a cobalt vinylidene species that adds to the alkene by a [2+2]-cycloaddition pathway. Ring-opening then occurs via outer-sphere β-O elimination assisted by coordination of a ZnX2 Lewis acid to the alkoxide leaving group. DFT models reveal that competing inner-sphere syn β-H and β-O elimination pathways are suppressed by the geometric constraints of the metallacycle intermediate. These models rationalize the observed stereochemical outcome of the reaction.

Catalytic Asymmetric Ring‐Opening Reactions of Unstrained Heterocycles Using Cobalt Vinylidenes

AbstractCobalt catalysts promote highly enantioselective ring‐opening reactions of 2,5‐dihydrofurans using vinylidenes. The products are acyclic organozinc compounds that can be functionalized with an electrophile. The proposed mechanism involves the generation of a cobalt vinylidene species that adds to the alkene by a [2+2]‐cycloaddition pathway. Ring‐opening then occurs via outer‐sphere β‐O elimination assisted by coordination of a ZnX2 Lewis acid to the alkoxide leaving group. DFT models reveal that competing inner‐sphere syn β‐H and β‐O elimination pathways are suppressed by the geometric constraints of the metallacycle intermediate. These models rationalize the observed stereochemical outcome of the reaction.

Cross- and Multi-Coupling Reactions Using Monofluoroalkanes.

Carbon-fluorine bonds are stable and have demonstrated sluggishness against various chemical manipulations. However, selective transformations of C-F bonds can be achieved by developing appropriate conditions as useful synthetic methods in organic chemistry. This review focuses on C-C bond formation at monofluorinated sp3 -hybridized carbons via C-F bond cleavage, including cross-coupling and multi-component coupling reactions. The C-F bond cleavage mechanisms on the sp3 -hybridized carbon centers can be primarily categorized into three types: Lewis acids promoted F atom elimination to generate carbocation intermediates; nucleophilic substitution with metal or carbon nucleophiles supported by the activation of C-F bonds by coordination of Lewis acids; and the cleavage of C-F bonds via a single electron transfer. The characteristic features of alkyl fluorides, in comparison with other (pseudo)halides as promising electrophilic coupling counterparts, are also discussed.

Square‐Planar Anionic Pt0Complexes

AbstractA T‐shaped Pt0complex with a diphosphine‐borane (DPB) ligand was prepared. The Pt→B interaction enhances the electrophilicity of the metal and triggers the addition of Lewis bases to give the corresponding tetracoordinate complexes. For the first time, anionic Pt0complexes are isolated and structurally authenticated. X‐ray diffraction analyses show the anionic complexes [(DPB)PtX]−(X=CN, Cl, Br, I) to be square‐planar. The d10configuration and Pt0oxidation state of the metal were unambiguously established by X‐ray photoelectron spectroscopy and DFT calculations. The coordination of Lewis acids as Z‐type ligands is a powerful mean to stabilize elusive electron‐rich metal complexes and achieve uncommon geometry.

Square-Planar Anionic Pt0 Complexes.

A T-shaped Pt0 complex with a diphosphine-borane (DPB) ligand was prepared. The Pt→B interaction enhances the electrophilicity of the metal and triggers the addition of Lewis bases to give the corresponding tetracoordinate complexes. For the first time, anionic Pt0 complexes are isolated and structurally authenticated. X-ray diffraction analyses show the anionic complexes [(DPB)PtX]- (X=CN, Cl, Br, I) to be square-planar. The d10 configuration and Pt0 oxidation state of the metal were unambiguously established by X-ray photoelectron spectroscopy and DFT calculations. The coordination of Lewis acids as Z-type ligands is a powerful mean to stabilize elusive electron-rich metal complexes and achieve uncommon geometry.

Concurrently Engineered Lewis Acid Sites and Coordination Sphere Vacancies in CoFe Prussian Blue Analogues for Boosted Bifunctional Oxygen Electrocatalysis

Prussian blue analogues (PBAs), due to their high surface area, large density of catalytically active sites, and high porosity, are one of the potential bifunctional oxygen electrocatalysts for industrial applications. However, so far, only limited success has been achieved toward developing highly efficient PBA-based electrocatalysts. Therefore, unravelling the underlying structure–property–activity relationship and designing strategies or combination of tested strategies are crucial to this effect. In this work, we demonstrate a strategy to concurrently engineer the coordination sphere vacancies and Lewis acid sites, via atomically dispersed Zn2+ dopants in CoFe PBA that makes Con+ more electropositive, to boost the bifunctional oxygen electrocatalysis on PBA surfaces. The optimal Zn-doping (3 mole %) not only enhances the oxygen evolution reaction (OER) activity of CoFe PBAs to the comparable level of the IrO2 catalyst but also depicts an impressive bifunctional oxygen activity with a low reversible overvoltage of 0.84 V. This work also demonstrates that an in situ formation of Co3+ (CoOOH) and Fe3+ (FeOOH) during the OER plays a crucial role for the boosted activity in bifunctional oxygen electrocatalysis. Besides providing highly efficient and low-cost catalysts, this study also imparts important insights to improve the efficiency of PBA-based bifunctional oxygen electrocatalysis.

Lewis acid-assisted reduction of nitrite to nitric and nitrous oxides via the elusive nitrite radical dianion.

Reduction of nitrite anions (NO2-) to nitric oxide (NO), nitrous oxide (N2O) and ultimately dinitrogen (N2) takes place in a variety of environments, including in the soil as part of the biogeochemical nitrogen cycle and in acidified nuclear waste. Nitrite reduction typically takes place within the coordination sphere of a redox-active transition metal. Here we show that Lewis acid coordination can substantially modify the reduction potential of this polyoxoanion to allow for its reduction under non-aqueous conditions (-0.74 V versus NHE). Detailed characterization confirms the formation of the borane-capped radical nitrite dianion (NO22-), which features a N(II) oxidation state. Protonation of the nitrite dianion results in the facile loss of nitric oxide (NO), whereas its reaction with NO results in disproportionation to nitrous oxide (N2O) and nitrite (NO2-). This system connects three redox levels in the global nitrogen cycle and provides fundamental insights into the conversion of NO2- to NO.

Highly sensitive sensing and quantitative detection of sulfate ion with a SERS chip-based on boric acid's Lewis effect.

Based on the Lewis acid's coordination principle, a surface-enhanced Raman scattering (SERS) chip strategy had been developed for the ultrasensitive quantitation of SO42-. Through the immobilization of silver nanoparticles (Ag NPs) and the construction of the boric acid-based sensing unit, the chip system displayed outstanding merits on the direct sensing of SO42-, e.g., simple operation, ultra-high sensitivity, reproducibility, excellent selectivity and specificity. Moreover, an accurate evaluation was obtained by ratiometric calculations on characteristic peaks (1382 and 1070cm-1) for quantitative detection of SO42-. The detection limit was down to 10nM. Tap water, beer, and mineral water samples were tested, and high recoveries were achieved (97.12-110.12%). Besides, such SERS chip also displayed strong applicability for the evaluation of SO32-. Therefore, this SERS chip provided a promising idea for the quantification of trace amounts of SO42- and SO32- in the fields of food safety and environmental monitoring.

The Close Interaction of a C−F Bond with an Amide Carbonyl: Crystallographic and Spectroscopic Characterization

AbstractThe putative interaction of a C−F bond with an amide carbonyl has been an intriguing topic of interest in this century for reasons spanning basic physical organic chemistry to biochemistry. However, to date, there exist no examples of a close, well‐defined interaction in which its unique aspects can be identified and exploited. Herein, we finally present an engineered system possessing an exceptionally tight C−F‐amide interaction, allowing us to obtain spectroscopic, crystallographic, and kinetic details of a distinctive, biochemically relevant chemical system for the first time. In turn, we also explore Lewis acid coordination, C−F bond promotion of amide isomerization, enantiomerization, and ion protonation processes.

The Close Interaction of a C-F Bond with an Amide Carbonyl: Crystallographic and Spectroscopic Characterization.

The putative interaction of a C−F bond with an amide carbonyl has been an intriguing topic of interest in this century for reasons spanning basic physical organic chemistry to biochemistry. However, to date, there exist no examples of a close, well‐defined interaction in which its unique aspects can be identified and exploited. Herein, we finally present an engineered system possessing an exceptionally tight C−F‐amide interaction, allowing us to obtain spectroscopic, crystallographic, and kinetic details of a distinctive, biochemically relevant chemical system for the first time. In turn, we also explore Lewis acid coordination, C−F bond promotion of amide isomerization, enantiomerization, and ion protonation processes.

Visible Light-Induced Regio- and Enantiodifferentiating [2 + 2] Photocycloaddition of 1,4-Naphthoquinones Mediated by Oppositely Coordinating 1,3,2-Oxazaborolidine Chiral Lewis Acid.

A range of asymmetric photochemical transformations using visible light have recently become considerably attractive. Among the various approaches, chiral Lewis acid association to enones for [2 + 2] and ortho photocycloadditions and oxadi-π-methane rearrangements have shown to be very promising. Naturally, chiral Lewis acid coordination protects one of the prochiral faces of the C═C double bond, which enables an effective enantiodifferentiation in the following bond-forming process(es). Here, we studied regio- and enantiodifferentiating [2 + 2] photocycloaddition reactions of naphthoquinone derivatives mediated by chiral oxazaborolidines. A stereochemical control was quite challenging for the 2-ene-1,4-dione substrate, as a double coordination of Lewis acid essentially cancels out the face selectivity, and a mono-coordination to each carbonyl group leads to an opposite stereochemical outcome. Furthermore, a stepwise coordination in the ground state of Lewis acid in a 1:1 fashion was practically inaccessible. We found that the excited-state decomplexation is a key to accomplish high regio- and enantioselectivities in the photocycloaddition of an ene-dione.

Impact of the coordination of multiple Lewis acid functions on the electronic structure and vn configuration of a metal center.

The covalent bond classification (CBC) method represents a molecule as MLlXxZz by evaluating the total number of L, X and Z functions interacting with M. The CBC method is a simplistic approach that is based on the notion that the bonding of a ligating atom (or group of atoms) can be expressed in terms of the number of electrons it contributes to a 2-electron bond. In many cases, the bonding in a molecule of interest can be described in terms of a 2-center 2-electron bonding model and the MLlXxZz classification can be derived straightforwardly by considering each ligand independently. However, the bonding within a molecule cannot always be described satisfactorily by using a 2-center 2-electron model and, in such situations, the MLlXxZz classification requires a more detailed consideration than one in which each ligand is treated in an independent manner. The purpose of this article is to provide examples of how the MLlXxZz classification is obtained in the presence of multicenter bonding interactions. Specific emphasis is given to the treatment of multiple π-acceptor ligands and the impact on the vn configuration, i.e. the number of formally nonbonding electrons on an element of interest.