ABSTRACT
Designing molecules that can undergo late-stage modifications resulting in specific optical properties is useful for developing structure-function trends in materials, which ultimately advance optoelectronic applications. Herein, we report a series of fused diborepinium ions stabilized by carbene and carbone ligands (diamino-N-heterocyclic carbenes, cyclic(alkyl)(amino) carbenes, carbodicarbenes, and carbodiphosphoranes), including a detailed bonding analysis. These are the first structurally confirmed examples of diborepin dications and we detail how distortions in the core of the pentacyclic fused system impact aromaticity, stability, and their light-emitting properties. Using the same fused diborepin scaffold, coordinating ligands were used to dramatically shift the emission profile, which exhibit colors ranging from blue to red (358-643 nm). Notably, these diborepinium ions access expanded regions of the visible spectrum compared to known examples of borepins, with quantum yields up to 60%. Carbones were determined to be superior stabilizing ligands, resulting in improved stability in the solution and solid states. Density functional theory was used to provide insight into the bonding as well as the specific transitions that result in the observed photophysical properties.
ABSTRACT
The effects of fixing the redox mediator (RM) reduction potential relative to a series of Cr-centered complexes capable of the reduction of CO2 to CO are disclosed. The greatest co-electrocatalytic activity enhancement is observed when the reduction potentials of the catalyst and RM are identical, implying that controlling the speciation of the Cr complex relative to RM activation is essential for improving catalytic performance. In all cases, the potential where co-catalytic activity is observed matches the reduction potential of the RM, regardless of the relative reduction potential of the Cr complex.
ABSTRACT
Fe(II) carboxylates react with dioxygen and carboxylic acid to form Fe6(µ-OH)2(µ3-O)2(µ-X)12(HX)2 (X = acetate or pivalate), which is an active oxidant for Rh-catalyzed arene alkenylation. Heating (150-200 °C) the catalyst precursor [(η2-C2H4)2Rh(µ-OAc)]2 with ethylene, benzene, Fe(II) carboxylate, and dioxygen yields styrene >30-fold faster than the reaction with dioxygen in the absence of the Fe(II) carboxylate additive. It is also demonstrated that Fe6(µ-OH)2(µ3-O)2(µ-X)12(HX)2 is an active oxidant under anaerobic conditions, and the reduced material can be reoxidized to Fe6(µ-OH)2(µ3-O)2(µ-X)12(HX)2 by dioxygen. At optimized conditions, a turnover frequency of â¼0.2 s-1 is achieved. Unlike analogous reactions with Cu(II) carboxylate oxidants, which undergo stoichiometric Cu(II)-mediated production of phenyl esters (e.g., phenyl acetate) as side products at temperatures ≥150 °C, no phenyl ester side product is observed when Fe carboxylate additives are used. Kinetic isotope effect experiments using C6H6 and C6D6 give k H/k D = 3.5(3), while the use of protio or monodeutero pivalic acid reveals a small KIE with k H/k D = 1.19(2). First-order dependencies on Fe(II) carboxylate and dioxygen concentration are observed in addition to complicated kinetic dependencies on the concentration of carboxylic acid and ethylene, both of which inhibit the reaction rate at a high concentration. Mechanistic studies are consistent with irreversible benzene C-H activation, ethylene insertion into the formed Rh-Ph bond, ß-hydride elimination, and reaction of Rh-H with Fe6(µ-OH)2(µ3-O)2(µ-X)12(HX)2 to regenerate a Rh-carboxylate complex.
ABSTRACT
We report the synthesis and characterization of a series of BNP-incorporated borafluorenate heterocycles formed via thermolysis reactions of pyridylphosphine and bis(phosphine)-coordinated borafluorene azides. The use of diphenyl-2-pyridylphosphine (PyPh2P), trans-1,2-bis(diphenylphosphino)ethylene (Ph2P(H)CâC(H)PPh2), and bis(diphenylphosphino)methane (Ph2PC(H2)PPh2) as stabilizing ligands resulted in Staudinger reactions to form complex heterocycles with four- (BN2P, BNPC, P2N2) and five-membered (BNP2C and BN2PC) rings, which were successfully isolated and fully characterized by multinuclear NMR and X-ray crystallography. However, when bis(diphenylphosphino)benzene (Ph2P-Ph-PPh2) was used as the ligand in a reaction with 9-bromo-9-borafluorene (BF-Br), due to the close proximity of the donor P atoms, the diphosphine-stabilized borafluoronium ion with an unusual borafluorene dibromide anion was formed. Reaction of the borafluoronium ion with trimethylsilyl azide left the cation intact, and the dibromide anion was substituted by a diazide. Density functional theory calculations were used to provide mechanistic insight into the formation of these new boracyclic compounds. This work highlights a new method in which donor phosphine ligands may be used to promote dimerization, cyclization, and ring contraction reactions to produce boracycles via Staudinger reactions.
ABSTRACT
For nearly a century, chemists have explored how transition-metal complexes can affect the physical and chemical properties of linear conjugated polyenes and heteropolyenes. While much has been written about higher hapticity complexes (η4-η6), less is known about the chemistry of their η2 analogues. Herein, we describe a general method for synthesizing 5,6-η2-(1-azatriene) tungsten complexes via a 6π-azaelectrocyclic dihydropyridine ring-opening that is promoted by the π-basic nature of {WTp(NO)(PMe3)}. This study includes detailed spectroscopic and crystallographic data for the η2-dihydropyridine and η2-1-azatriene complexes, both of which were prepared as single regio- and stereoisomers.
ABSTRACT
The catalytic reduction of dioxygen (O2) is important in biological energy conversion and alternative energy applications. In comparison to Fe- and Co-based systems, examples of catalytic O2 reduction by homogeneous Mn-based systems is relatively sparse. Motivated by this lack of knowledge, two Mn-based catalysts for the oxygen reduction reaction (ORR) containing a bipyridine-based non-porphyrinic ligand framework have been developed to evaluate how pendent proton donor relays alter activity and selectivity for the ORR, where Mn(p-tbudhbpy)Cl (1) was used as a control complex and Mn(nPrdhbpy)Cl (2) contains a pendent -OMe group in the secondary coordination sphere. Using an ammonium-based proton source, N,N'-diisopropylethylammonium hexafluorophosphate, we analyzed catalytic activity for the ORR: 1 was found to be 64% selective for H2O2 and 2 is quantitative for H2O2, with O2 binding to the reduced Mn(ii) center being the rate-determining step. Upon addition of the conjugate base, N,N'-diisopropylethylamine, the observed catalytic selectivity of both 1 and 2 shifted to H2O as the primary product. Interestingly, while the shift in selectivity suggests a change in mechanism for both 1 and 2, the catalytic activity of 2 is substantially enhanced in the presence of base and the rate-determining step becomes the bimetallic cleavage of the O-O bond in a Mn-hydroperoxo species. These data suggest that the introduction of pendent relay moieties can improve selectivity for H2O2 at the expense of diminished reaction rates from strong hydrogen bonding interactions. Further, although catalytic rate enhancements are observed with a change in product selectivity when base is added to buffer proton activity, the pendent relays stabilize dimer intermediates, limiting the maximum rate.
ABSTRACT
Neutral 1-boraphenalene displays the isoelectronic structure of the phenalenyl carbocation and is expected to behave as an attractive organoboron multi-redox system. However, the isolation of new redox states have remained elusive even though the preparation of neutral boron(III)-containing phenalene compounds have been extensively studied. Herein, we have adopted an N-heterocyclic carbene ligand stabilization approach to achieve the first isolation of the stable and ambipolar 1-boraphenalenyl radical 1â¢. The 1-boraphenalenyl cation 1+ and anion 1- have also been electrochemically observed and chemically isolated, representing new redox forms of boraphenalene for the study of non-Kekulé polynuclear benzenoid molecules. Experimental and theoretical investigations suggest that the interconvertible three-redox-state species undergo reversible electronic structure modifications, which primarily take place on the polycyclic framework of the molecules, exhibiting atypical behavior compared to known donor-stabilized organoboron compounds. Initial reactivity studies, aromaticity evaluations, and photophysical studies show redox-state-dependent trends. While 1+ is luminescent in both the solution and solid states, 1⢠exhibits boron-centered reactivity and 1- undergoes substitution chemistry on the boraphenalenyl skeleton and serves as a single-electron transfer reductant.
ABSTRACT
Systems that possess open- and closed-shell behavior attract significant attention from researchers due to their inherent redox and charge transport properties. Herein, we report the synthesis of the first diborepin biradicals. They display tunable biradical character based on the steric and electronic profile of the stabilizing ligand and the resulting geometric deviation of the diborepin core from planarity. While there are numerous all-carbon-based biradical systems, boron-based biradical compounds are comparatively rare, particularly ones in which the radical sites are disjointed. Calculations using density functional theory (DFT) and multireference methods demonstrate that the fused diborepin scaffold exhibits high biradical character, up to 95%. Use of a nonsterically demanding diaminocarbene promotes the planarization of the pentacyclic framework, resulting in the synthetic realization of a diborepin containing a dibora-quinoidal core, which possesses a closed-shell ground state and thermally accessible triplet state. The biradicals were structurally authenticated and characterized by both solution and solid-state electron paramagnetic resonance (EPR) spectroscopy. Half-field transitions were observed at low temperatures (about 170 K), confirming the presence of the triplet state. Initial reactivity studies of the biradicals led to the isolation and structural characterization of bis(borepin hydride) and bis(borepin dianion).
ABSTRACT
Medicinal chemists use vast combinatorial molecular libraries to develop leads for new pharmaceuticals. The syntheses of these compounds typically rely on coupling molecular fragments through atoms with planar (sp2) geometry. These so-called flat molecules often lack the protein binding site specificity needed to be an effective drug. Here, we demonstrate a coupling strategy in which a cyclohexene is used as a linker to connect two diverse molecular fragments while forming two new tetrahedral (sp3) stereocenters. These connections are made with the aid of a tungsten complex that activates anisole toward an unusual double protonation, followed by sequential nucleophilic additions. As a result, either cis- or trans-disubstituted cyclohexenes can be prepared with a range of chemical diversity unparalleled by other dearomatization methods.
ABSTRACT
The non-bonding carbone lone pair in geometrically-constrained antimony and bismuth carbodiphosphorane complexes readily complexed AuCl to afford rare examples of geminal bimetallic carbone coordination featuring a main-group metal.
ABSTRACT
Substitution of a C=C bond by an isoelectronic B-N bond is a well-established strategy to alter the electronic structure and stability of acenes. BN-substituted acenes that possess narrow energy gaps have attractive optoelectronic properties. However, they are susceptible to air and/or light. Here we present the design, synthesis and molecular structures of fully π-conjugated cationic BN-doped acenes stabilized by carbodicarbene ligands. They are luminescent in the solution and solid states and show high air and moisture stability. Compared with their neutral BN-substituted counterparts as well as the parent all-carbon acenes, these species display improved quantum yields and small optical gaps. The electronic structures of the azabora-anthracene and azabora-tetracene cations resemble higher-order acenes while possessing high photo-oxidative resistance. Investigations using density functional theory suggest that the stability and photo-physics of these conjugated systems may be ascribed to their cationic nature and the electronic properties of the carbodicarbene.
ABSTRACT
Due to its efficacy as a dopamine receptor agonist, methylphenidate (MPH) is of interest as a potential therapeutic for cocaine addiction. While numerous derivatives of MPH have been investigated for their potential medicinal value, functionalization of the piperidine ring has not been explored. The pyridine borane ligand in WTp(NO)(PMe3)(η2-pyBH3) is dearomatized by the metal and can be elaborated to the analogous η2-mesylpyridinium complex. Installing a methyl phenylacetate moiety at the C2' position via a Reformatsky reaction followed by a tandem protonation/nucleophilic addition sequence results in a library of erythro MPH analogues functionalized at the piperidyl C5' position. The functional group is added chemoselectively to C5', cis to the methyl phenylacetate. Repeating this procedure with an enantioenriched source of the tungsten reagent results in enantioenriched MPH derivatives. All identities of the newly reported compounds are supported by comprehensive 2D NMR and HRMS data or crystallographic data.
ABSTRACT
Selective and site-specific boron-doping of polycyclic aromatic hydrocarbon frameworks often give rise to redox and/or photophysical properties that are not easily accessible with the analogous all-carbon systems. Herein, we report ligand-mediated control of boraphenanthrene closed- and open-shell electronic states, which has led to the first structurally characterized examples of neutral bis(9-boraphenanthrene) (2-3) and its corresponding biradical (4). Notably, compounds 2 and 3 show intramolecular charge transfer absorption from the 9-boraphenanthrene units to p-quinodimethane, exhibiting dual (red-shifted) emission in solution due to excited state conjugation enhancement (ESCE). Moreover, while boron-centered monoradicals are ubiquitous, biradical 4 represents a rare type of open-shell singlet compound with 95% biradical character, among the highest of any reported boron-based polycyclic species with two radical sites.
ABSTRACT
A series of BN-incorporated borafluorenate heterocycles, bis(borafluorene-phosphinimine)s (11-15), have been formed via intramolecular Staudinger-type reactions. The reactions were promoted by light or heat using monodentate phosphine-stabilized 9-azido-9-borafluorenes (R3P-BF-N3; 6-10) and involve the release of dinitrogen (N2), migration of phosphine from boron to nitrogen, and oxidation of the phosphorus center (PIII to PV). Density functional theory (DFT) calculations provide mechanistic insight into the formation of these compounds. Compounds 11-15 are blue emissive in the solution and solid states with absolute quantum yields (ΦF) ranging from 12 to 68%.
ABSTRACT
Friedel-Crafts Arylation (the Scholl reaction) is the coupling of two aromatic rings with the aid of a strong Lewis or Brønsted acid. This historically significant C-C bond forming reaction normally leads to aromatic products, often as oligomeric mixtures, dictated by the large stabilization gained upon their rearomatization. The coordination of benzene by a tungsten complex disrupts the natural course of this reaction sequence, allowing for Friedel-Crafts Arylation without rearomatization or oligomerization. Subsequent addition of a nucleophile to the coupled intermediate leads to functionalized cyclohexenes. In this work, we show that by coordinating benzene to tungsten through two carbons (dihapto-coordinate), a rarely observed double protonation of the bound benzene is enabled, allowing its subsequent coupling to a second arene without the need of a precious metal or Lewis acid catalyst.
ABSTRACT
A Zn2+ based complex, 3, displays greatly increased fluorescence emission in the presence of Mg2+. Fluorescent and computational studies suggest that 3 selectively interacts with Mg2+ due to optimal cavity size formation between two uncoordinated pyrazole side arms. This work thus represents a new approach to the development of fluorescent chemosensors.
ABSTRACT
The syntheses, molecular structures, reactivities, and computational assessment of dipotassium diboratapentacene isomers are described (1 and 2). These compounds represent the first examples of aromatized diboraacenes where the boron atoms are spatially separated in different rings of the acene framework. Both 1 and 2 react with carbon dioxide (CO2) via diastereoselective carboxylation of the pentacene backbone that likely proceeds by a frustrated Lewis pair-like mechanism. The placement of the boron atoms and the reactivity studies provide a platform for later stage functionalization of diboraacenes beyond the central ring of the polycyclic aromatic hydrocarbon core.
ABSTRACT
The addition of non-benzenoid quinones, acenapthenequinone or aceanthrenequinone, to the 9-carbene-9-borafluorene monoanion (1) affords the first examples of dianionic 10-membered bora-crown ethers (2-5), which are characterized by multi-nuclear NMR spectroscopy (1 H, 13 C, 11 B), X-ray crystallography, elemental analysis, and UV/Vis spectroscopy. These tetraoxadiborecines have distinct absorption profiles based on the positioning of the alkali metal cations. When compound 4, which has a vacant C4 B2 O4 cavity, is reacted with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, a color change from purple to orange serves as a visual indicator of metal binding to the central ring, whereby the Na+ ion coordinates to four oxygen atoms. A detailed theoretical analysis of the calculated reaction energetics is provided to gain insight into the reaction mechanism for the formation of 2-5. These data, and the electronic structures of proposed intermediates, indicate that the reaction proceeds via a boron enolate intermediate.
ABSTRACT
We report the dimerization and oligomerization of ethylene using bis(phosphino)boryl supported Ni(II) complexes as catalyst precursors. By using alkylaluminum(III) compounds or other Lewis acid additives, Ni(II) complexes of the type (RPBP)NiBr (R = tBu or Ph) show activity for the production of butenes and higher olefins. Optimized turnover frequencies of 640 molethylene·molNi-1·s-1 for the formation of butenes with 41(1)% selectivity for 1-butene using (PhPBP)NiBr, and 68 molethylene·molNi-1·s-1 for butenes production with 87.2(3)% selectivity for 1-butene using (tBuPBP)NiBr, have been demonstrated. With methylaluminoxane as a co-catalyst and (tBuPBP)NiBr as the precatalyst, ethylene oligomerization to form C4 through C20 products was achieved, while the use of (PhPBP)NiBr as the pre-catalyst retained selectivity for C4 products. Our studies suggest that the ethylene dimerization is not initiated by Ni hydride or alkyl intermediates. Rather, our studies point to a mechanism that involves a cooperative B/Ni activation of ethylene to form a key 6-membered borametallacycle intermediate. Thus, a cooperative activation of ethylene by the Ni-B unit of the (RPBP)Ni catalysts is proposed as a key element of the Ni catalysis.