Pushing the Limits of Organometallic Redox Chemistry with an Isolable Mn(-I) Dianion.

We report an incredibly reducing and redox-active Mn-I dianion, [Mn(CO)3(Ph2B(tBuNHC)2)]2- (NHC = N-heterocyclic carbene), furnished via 2e- reduction of the parent 16e- MnI complex with Na0 or K0. Cyclic voltammograms show a Mn0/-I redox couple at -3.13 V vs Fc+/0 in tetrahydrofuran (THF), -3.06 V in 1,2-dimethoxyethane, and -2.85 V in acetonitrile. The diamagnetic Mn-I dianion is stable in solution and solid-state at room temperature, tolerating a wide range of countercations ([M(2.2.2)crypt]+, [M(18-crown-6)]+, [nBu4N]+; M = Na, K). Countercation identity does not significantly alter 13C NMR spectral signatures with [nBu4N]+ and Na+, suggesting minimal ion pairing in solution. IR spectroscopy reveals a significant decrease in CO stretching frequencies from MnI to Mn-I (ca. 240 cm-1), consistent with a drastic increase in electron density at Mn. State-of-the-art DFT calculations are in excellent agreement with the observed IR spectral data. Moreover, the Mn-I dianion behaves as a chemical reductant, smoothly releasing 1e- or 2e- to regenerate the oxidized Mn0 or MnI species in solution. The reducing potential of [Mn(CO)3(Ph2B(tBuNHC)2)]2- surpasses the naphthalenide anion in THF (-3.09 V) and represents one of the strongest isolable chemical redox agents.

Organocatalytic Enantioselective [1,2]-Stevens Rearrangement of Azetidinium Salts.

The first organocatalyzed enantioselective [1,2]-Stevens rearrangement is reported. 4-Alkylideneproline derivatives are produced in up to 86% yield and in up to 90:10 er, with recrystallization enhancing er up to >99.5:0.5. Product configuration was opposite that predicted by existing stereochemical models for this organocatalyst class, and DFT calculations revealed a novel mode of asymmetric induction. The adaptability of this catalytic strategy for asymmetric [1,2]-Stevens rearrangements of other heterocyclic amines was demonstrated.

Wingtip-Flexible N-Heterocyclic Carbenes: Unsymmetrical Connection between IMes and IPr.

IMes (IMes=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) and IPr (IPr=1,3- bis(2,6-diisopropylphenyl)imidazol-2-ylidene) represent by far the most frequently used N-heterocyclic carbene ligands in homogeneous catalysis, however, despite numerous advantages, these ligands are limited by the lack of steric flexibility of catalytic pockets. We report a new class of unique unsymmetrical N-heterocyclic carbene ligands that are characterized by freely-rotatable N-aromatic wingtips in the imidazol-2-ylidene architecture. The combination of rotatable N-CH2 Ar bond with conformationally-fixed N-Ar linkage results in a highly modular ligand topology, entering the range of geometries inaccessible to IMes and IPr. These ligands are highly reactive in Cu(I)-catalyzed ß-hydroboration, an archetypal borylcupration process that has had a transformative impact on the synthesis of boron-containing compounds. The most reactive Cu(I)-NHC in this class has been commercialized in collaboration with MilliporeSigma to enable broad access of the synthetic chemistry community. The ligands gradually cover %Vbur geometries ranging from 37.3 % to 52.7 %, with the latter representing the largest %Vbur described for an IPr analogue, while retaining full flexibility of N-wingtip. Considering the modular access to novel geometrical space in N-heterocyclic carbene catalysis, we anticipate that this concept will enable new opportunities in organic synthesis, drug discovery and stabilization of reactive metal centers.

Near-Infrared Emissive B-N Lewis Pair-Functionalized Anthracenes via Selective LUMO Delocalization in Extended Conjugated Dimer and Polymer.

Acenes are attractive as building blocks for low gap organic materials with applications, for example, in organic light emitting diodes, solar cells, bioimaging and diagnostics. Previously, we have shown that modification of dipyridylanthracene via B-N Lewis pair fusion (BDPA) strongly redshifts the emission, while facilitating self-sensitized reactivity toward O2 to reversibly generate the corresponding endoperoxides. Herein, we report on the further expansion of the p-system of BDPA to a vinyl-substituted monomer, vinylene-bridged dimer, and a polymer with an average of 20 chromophores. The extension of π-conjugation results in largely reduced band gaps of 1.8 eV for the dimer and 1.7 eV for the polymer, the latter giving rise to NIR emission with a maximum at 731 nm and an appreciable quantum yield of 7%. Electrochemical and computational studies reveal efficient delocalization of the lowest unoccupied molecular orbital (LUMO) along the pyridyl-anthracene-pyridyl axis, which results in effective electronic communication between BDPA units, selectively lowers the LUMO, and ultimately narrows the band gap. Time-resolved emission and transient absorption (TA) measurements offer insights into the pertinent photophysical processes. Extension of π-conjugation also slows down the self-sensitized formation of endoperoxides, while significantly accelerating the thermal release of singlet oxygen to regenerate the parent acenes.

Synthesis and Structure-Property Relationships in Regioisomeric Alternating Borane-Terthiophene Polymers.

Main-chain boron-containing π-conjugated polymers are attractive for organic electronic, sensing, and imaging applications. Alternating terthiophene-borane polymers were prepared and the effects of regioisomeric attachment of the conjugated linker and variations in the electronic effect of the pendent aryl groups (2,4,6-tri-tert-butylphenyl, Mes*; 2,4,6-tris(trifluoromethyl)phenyl, FMes) examined. Pd2 dba3 /P(t-Bu)3 -catalyzed Stille polymerization of arylbis(2-thienyl)borane and arylbis(3-thienylborane) with 2,5-bis(trimethylstannyl)thiophene at 120 °C gave polymers with appreciable molecular weight but MALDI-TOF MS analyses showed evidence of unusually prominent homocoupling. These defects could be suppressed by using brominated rather than iodinated monomers, more hindered 2,5-bis(tri-n-butylstannyl)thiophene as comonomer, and Pd2 dba3 /P(o-tol)3 as the catalyst at 100 °C. Under these conditions, macrocyclic species with n=3-10 repeating units formed preferentially according to MALDI-TOF MS analyses. Photophysical studies revealed a prominent effect of the regiochemistry and the nature of the pendent aryl groups on the absorption and emission, giving rise to orange, yellow-green, blue-green, and blue emissive materials respectively. The electronic effects were rationalized through DFT calculations on bis(terthiophene) model systems.

[IPr#-PEPPSI]: A Well-Defined, Highly Hindered and Broadly Applicable Pd(II)-NHC (NHC = N-Heterocyclic Carbene) Precatalyst for Cross-Coupling Reactions.

In this Special Issue, "Featured Papers in Organometallic Chemistry", we report on the synthesis and characterization of [IPr#-PEPPSI], a new, well-defined, highly hindered Pd(II)-NHC precatalyst for cross-coupling reactions. This catalyst was commercialized in collaboration with MilliporeSigma, Burlington, ON, Canada (no. 925489) to provide academic and industrial researchers with broad access to reaction screening and optimization. The broad activity of [IPr#-PEPPSI] in cross-coupling reactions in a range of bond activations with C-N, C-O, C-Cl, C-Br, C-S and C-H cleavage is presented. A comprehensive evaluation of the steric and electronic properties is provided. Easy access to the [IPr#-PEPPSI] class of precatalysts based on modular pyridine ligands, together with the steric impact of the IPr# peralkylation framework, will facilitate the implementation of well-defined, air- and moisture-stable Pd(II)-NHC precatalysts in chemistry research.

L-Shaped Heterobidentate Imidazo[1,5-a]pyridin-3-ylidene (N,C)-Ligands for Oxidant-Free AuI /AuIII Catalysis.

In the last decade, major advances have been made in homogeneous gold catalysis. However, AuI /AuIII catalytic cycle remains much less explored due to the reluctance of AuI to undergo oxidative addition and the stability of the AuIII intermediate. Herein, we report activation of aryl halides at gold(I) enabled by NHC (NHC=N-heterocyclic carbene) ligands through the development of a new class of L-shaped heterobidentate ImPy (ImPy=imidazo[1,5-a]pyridin-3-ylidene) N,C ligands that feature hemilabile character of the amino group in combination with strong σ-donation of the carbene center in a rigid conformation, imposed by the ligand architecture. Detailed characterization and control studies reveal key ligand features for AuI /AuIII redox cycle, wherein the hemilabile nitrogen is placed at the coordinating position of a rigid framework. Given the tremendous significance of homogeneous gold catalysis, we anticipate that this ligand platform will find widespread application.

Near-Infrared-Absorbing B-N Lewis Pair-Functionalized Anthracenes: Electronic Structure Tuning, Conformational Isomerism, and Applications in Photothermal Cancer Therapy.

B-N-fused dianthracenylpyrazine derivatives are synthesized to generate new low gap chromophores. Photophysical and electrochemical, crystal packing, and theoretical studies have been performed. Two energetically similar conformers are identified by density functional theory calculations, showing that the core unit adopts a curved saddle-like shape (x-isomer) or a zig-zag conformation (z-isomer). In the solid state, the z-isomer is prevalent according to an X-ray crystal structure of a C6F5-substituted derivative (4-Pf), but variable-temperature nuclear magnetic resonance studies suggest a dynamic behavior in solution. B-N fusion results in a large decrease of the HOMO-LUMO gap and dramatically lowers the LUMO energy compared to the all-carbon analogues. 4-Pf in particular shows significant absorbance at greater than 700 nm while being almost transparent throughout the visible region. After encapsulation in the biodegradable polymer DSPE-mPEG2000, 4-Pf nanoparticles (4-Pf-NPs) exhibit good water solubility, high photostability, and an excellent photothermal conversion efficiency of ∼41.8%. 4-Pf-NPs are evaluated both in vitro and in vivo as photothermal therapeutic agents. These results uncover B-N Lewis pair functionalization of PAHs as a promising strategy toward new NIR-absorbing materials for photothermal applications.

Coordination-Induced Weakening of a C(sp3)-H Bond: Homolytic and Heterolytic Bond Strength of a CH-Ni Agostic Interaction.

The scission of a C(sp3)-H bond to form a new metal-alkyl bond is a fundamental step in coordination chemistry and catalysis. However, the extent of C-H bond weakening when this moiety interacts with a transition metal is poorly understood and quantifying this phenomenon could provide insights into designing more efficient C-H functionalization catalysts. We present a nickel complex with a robust adamantyl reporter ligand that enables the measurement of C-H acidity (pKa) and bond dissociation free energy (BDFE) for a C(sp3)-H agostic interaction, showing a decrease in pKa by dozens of orders of magnitude and BDFE decrease of about 30 kcal/mol upon coordination. X-ray crystallographic data is provided for all molecules, including a distorted square planar NiIII metalloradical and "doubly agostic" NiII(κ2-CH2) complex.

DyKAT by DiCat: Stereoconvergent Dienamine-Catalyzed Claisen Rearrangements.

This Claisen rearrangement establishes the feasibility of DyKAT of γ-epimeric enals via dienamine formation to afford enantioenriched products. γ-Aryl and -alkyl enals, and exocyclic enals that introduce quaternary centers, are all amenable substrates. Products are readily converted into pyrrolidines or cyclopentenols. Notably, a reactive dienamine intermediate has been isolated from a catalytic reaction, fully characterized, and converted to product upon reexposure to reaction conditions. Product configuration arises from a directing C-H···π interaction in the transition state.

Linear Extension of Anthracene via B←N Lewis Pair Formation: Effects on Optoelectronic Properties and Singlet O2 Sensitization.

The functionalization of polycyclic aromatic hydrocarbons (PAHs) via B←N Lewis pair formation offers an opportunity to judiciously fine-tune the structural features and optoelectronic properties, to suit the demands of applications in organic electronic devices, bioimaging, and as sensitizers for singlet oxygen generation. We demonstrate that the N-directed electrophilic borylation of 2,6-di(pyrid-2-yl)anthracene offers access to linearly extended acene derivatives Py-BR (R=Et, Ph, C6 F5 ). In comparison to indeno-fused 9,10-diphenylanthracene, the formal "BN for CC" replacement in Py-BR selectively lowers the LUMO, resulting in a much reduced HOMO-LUMO gap. An even more extended conjugated system with seven six-membered rings in a row (Qu-BEt) is obtained by borylation of 2,6-di(quinolin-8-yl)anthracene. Fluorinated Py-BPf shows particularly advantageous properties, including relatively lower-lying HOMO and LUMO levels, strong yellow-green fluorescence, and effective singlet oxygen sensitization, while resisting self-sensitized conversion to its endoperoxide.

Structures of the Most Twisted Thioamide and Selenoamide: Effect of Higher Chalcogens of Twisted Amides on N-C(X) Resonance.

Amide bond replacement with planar isosteric chalcogen analogues has an important implication for the properties of the N-C(X) linkage in structural chemistry, biochemistry and organic synthesis. Herein, we report the first higher chalcogen derivatives of non-planar twisted amides. The synthesis of twisted thioamide in a versatile system has been accomplished by direct thionation without cleavage of the σ N-C bond. The synthesis of twisted selenoamide has been accomplished by selenation with Woollins' reagent. The structures of higher chalcogen analogues of non-planar amides were unambiguously confirmed by X-ray crystallography. Reactivity studies were conducted to determine the effect of isologous N-C(O) to N-C(X) replacement on the properties of the amide linkage. Computational studies were employed to evaluate structural and energetic parameters of amide bond alteration in higher chalcogen amides. The study provides the first experimental evidence on the effect of chalcogen isologues on the structural and electronic properties of the non-planar amide N-C(X) linkage.

[(NHC)PdCl2(Aniline)] Complexes: Easily Synthesized, Highly Active Pd(II)-NHC Precatalysts for Cross-Coupling Reactions.

We report the synthesis, characterization, and reactivity of [(NHC)PdCl2(aniline)] complexes. These well-defined, air- and moisture-stable catalysts are highly active in the Suzuki-Miyaura cross-coupling of amides by N-C(O) activation as well as in the Suzuki-Miyaura cross-coupling of esters, aryl chlorides, and Buchwald-Hartwig amination. Most crucially, this study introduces broadly available anilines as stabilizing ligands for well-defined Pd(II)-NHC catalysts. The availability of various aniline scaffolds, including structural and electronic diversity, has a significant potential in fine-tuning of challenging cross-couplings by Pd-NHCs. The parent catalyst in this class, [Pd(IPr)(AN)Cl2], has been commercialized in collaboration with Millipore Sigma, offering broad access for reaction screening and optimization.

Evaluation of Cyclic Amides as Activating Groups in N-C Bond Cross-Coupling: Discovery of N-Acyl-δ-valerolactams as Effective Twisted Amide Precursors for Cross-Coupling Reactions.

The development of efficient methods for facilitating N-C(O) bond activation in amides is an important objective in organic synthesis that permits the manipulation of the traditionally unreactive amide bonds. Herein, we report a comparative evaluation of a series of cyclic amides as activating groups in amide N-C(O) bond cross-coupling. Evaluation of N-acyl-imides, N-acyl-lactams, and N-acyl-oxazolidinones bearing five- and six-membered rings using Pd(II)-NHC and Pd-phosphine systems reveals the relative reactivity order of N-activating groups in Suzuki-Miyaura cross-coupling. The reactivity of activated phenolic esters and thioesters is evaluated for comparison in O-C(O) and S-C(O) cross-coupling under the same reaction conditions. Most notably, the study reveals N-acyl-δ-valerolactams as a highly effective class of mono-N-acyl-activated amide precursors in cross-coupling. The X-ray structure of the model N-acyl-δ-valerolactam is characterized by an additive Winkler-Dunitz distortion parameter Σ(τ+χN) of 54.0°, placing this amide in a medium distortion range of twisted amides. Computational studies provide insight into the structural and energetic parameters of the amide bond, including amidic resonance, N/O-protonation aptitude, and the rotational barrier around the N-C(O) axis. This class of N-acyl-lactams will be a valuable addition to the growing portfolio of amide electrophiles for cross-coupling reactions by acyl-metal intermediates.

Ligand Protonation at Carbon, not Nitrogen, during H2 Production with Amine-Rich Iron Electrocatalysts.

We present monometallic H2 production electrocatalysts containing electron-rich triamine-cyclopentadienyl (Cp) ligands coordinated to iron. After selective CO extrusion from the iron tricarbonyl precursors, electrocatalysis is observed via cyclic voltammetry in the presence of an exogenous acid. Contrary to the fact that amines in the secondary coordination sphere are often protonated during electrocatalysis, comprehensive quantum-chemical calculations indicate that the amines likely do not function as proton relays; instead, endo-Cp ring protonation is most favorable after 1e- reduction. This unusual mechanistic pathway emphasizes the need to consider a broad domain of H+/e- addition products by synergistically combining experimental and theoretical resources.

Electrochromic Polycationic Organoboronium Macrocycles with Multiple Redox States.

Polycationic macrocycles are attractive as they display unique molecular switching capabilities arising from their redox properties. Although diverse polycationic macrocycles have been developed, those based on cationic boron systems remain very limited. We present herein the development of novel polycationic macrocycles by introducing organoboronium moieties into a conjugated organoboron macrocyclic framework. These macrocycles consist of four bipyridylboronium units that are connected by fluorene and either electron-deficient arylborane or electron-rich arylamine moieties. Electrochemical studies reveal that the macrocycles undergo reversible multi-step redox processes with transfer of up to 10 electrons. Switchable electrochromic behavior is demonstrated via spectroelectrochemical studies and the observed color changes are rationalized by correlation with computed electronic transitions using DFT methods.

ROMP-Boranes as Moisture-Tolerant and Recyclable Lewis Acid Organocatalysts.

Although widely used in catalysis, the multistep syntheses and high loadings typically employed are limiting broader implementation of highly active tailor-made arylborane Lewis acids and Lewis pairs. Attempts at developing recyclable systems have thus far met with limited success, as general and versatile platforms are yet to be developed. We demonstrate a novel approach that is based on the excellent control and functional group tolerance of ring-opening metathesis polymerization (ROMP). The ROMP of highly Lewis acidic borane-functionalized phenylnorbornenes afforded both a soluble linear copolymer and a cross-linked organogel. The polymers proved highly efficient as recyclable catalysts in the reductive N-alkylation of arylamines under mild conditions and at exceptionally low catalyst loadings. The modular design presented herein can be readily adapted to other finely tuned triarylboranes, enabling wide applications of ROMP-borane polymers as well-defined supported organocatalysts.

N-Acyl-glutarimides: Effect of Glutarimide Ring on the Structures of Fully Perpendicular Twisted Amides and N-C Bond Cross-Coupling.

N-Acyl-glutarimides have emerged as the most reactive precursors for N-C(O) bond cross-coupling reactions to date, wherein the reactivity is driven by ground-state destabilization of the amide bond. Herein, we report a full study on the effect of a glutarimide ring on the structures, electronic properties, and reactivity of fully perpendicular N-acyl-glutarimide amides. Most notably, this report demonstrates the generality of deploying N-acyl-glutarimides to achieve full twist of the acyclic amide bond, and results in the discovery of N-acyl-glutarimide amide with an almost perfect twist value, τ = 89.1°. X-ray structures of five new N-acyl-glutarimides are reported. Reactivity studies in the Suzuki-Miyaura cross-coupling and transamidation reactions provide insight into the reactivity of N-acyl-glutarimides in metal-catalyzed and transition-metal-free reactions. The effect of distortion, structures, and rotational barriers around the N-C(O) axis is discussed. The ability to achieve full distortion of the amide bond significantly expands the range of reagents available for N-C(O) cross-coupling reactions.

Enhancing the Acceptor Character of Conjugated Organoborane Macrocycles: A Highly Electron-Deficient Hexaboracyclophane.

We introduce a new boron-doped cyclophane, the hexabora[16 ]cyclophane B6-F Mes, in which six tricoordinate borane moieties alternate with short conjugated p-phenylene linkers. Exocyclic 2,4,6-tris(trifluoromethyl)phenyl (F Mes) groups serve not only to further withdraw electron density but at the same time sterically shield the boron atoms, resulting in a macrocycle that is both highly electron-deficient and stable. The optical and electronic properties are compared with those of related linear oligomers and the electronic structure is further evaluated by computational methods. The studies uncover unique properties of B6-F Mes, including a low-lying and extensively delocalized LUMO and a wide HOMO-LUMO gap, which arise from the combination of a cyclic π-system, strong electronic communication between the closely spaced borons, and the attachment of electron-deficient pendent groups. The binding of small anions to the electron-deficient macrocycle and molecular model compounds is investigated and emissive exciplexes are detected in aromatic solvents.

Tuning the Structure and Electronic Properties of B-N Fused Dipyridylanthracene and Implications on the Self-Sensitized Reactivity with Singlet Oxygen.

We demonstrate that the modification of anthracene with B ← N Lewis pairs at their periphery serves as a highly effective tool to modify the electronic structure with important ramifications on the generation and reactivity toward singlet oxygen. A series of BN-fused dipyridylanthracenes with Me groups in different positions of the pyridyl ring have been prepared via directed electrophilic borylation. The steric and electronic effects of the substituents on the structural features and electronic properties of the isomeric borane-functionalized products have been investigated in detail, aided by experimental tools and computational studies. We find that BDPA-2Me, with Me groups adjacent to the pyridyl N, has the longest B-N distance and shows overall less structural distortions, whereas BDPA-5Me with the Me group close to the anthracene backbone experiences severe distortions that are reflected in the buckling of the anthracene framework and dislocation of the boron atoms from the planes of the phenyl rings they are attached to. The substitution pattern also has a dramatic effect on the self-sensitized reactivity of the acenes toward O2 and the thermal release of singlet oxygen from the respective endoperoxides. Kinetic analyses reveal that BDPA-2Me rapidly reacts with O2, whereas BDPA-5Me is converted only very slowly to its endoperoxide. However, the latter serves as an effective singlet oxygen sensitizer, as demonstrated in the preferential formation of the endoperoxide of dimethylanthracene in a competition experiment. These results demonstrate that even relatively small modifications in the substitution of the pyridyl ring of BN-fused dipyridylanthracenes change the steric and electronic structure, resulting in dramatically different reactivity patterns. Our findings provide important guidelines for the design of highly effective sensitizers for singlet oxygen on one hand and the realization of materials that readily form endoperoxides in a self-sensitized manner and then thermally release singlet oxygen on demand on the other hand.