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The first structurally characterized example of a trioxaborinanone (

Borole-doped polycyclic aromatic hydrocarbons (PAHs) have garnered attention in recent years due to their attractive photophysical properties and potential utility in electronic devices. In this work, a borole-doped PAH, 12-boradibenzofluorene, is synthesized and formal intermolecular nitrene and oxygen atom insertion reactions were employed to access 1,2-azaborine- and 1,2-oxaborine-containing analogues of the carbonaceous PAH pentaphene. Iodosobenzene is established as a versatile reagent for oxygen atom insertion reactions into a variety of borole species to access 1,2-oxaborine systems.

PhIBrsub2/sub, first purported to exist over 100 years ago, has been subject of few reports due to its low stability. However, a recent publication proposes a reaction of PIFA (PhI(OC(O)-CFsub3/sub)sub2/sub) with TMSBr to form PhIBrsub2/subiin situ/iand demonstrated its efficacy in aryl brominations. This report investigates this synthesis by replicating bromination reactions claiming to useiin situ/iPhIBrsub2/subas described. The spectroscopical and computational results indicate formation of PhI and Brsub2/subwhere Brsub2/subis responsible for bromination and no supporting evidence for invoking PhIBrsub2/subas an intermediate is found.

A benchmark density functional theory (DFT) study of 1H NMR chemical shifts for data sets comprising 200 chemical shifts, including complex natural products, has been carried out to assess the performance of DFT methods. Two new benchmark data sets, NMRH33 and NMRH148, have been established. The meta-GGA revTPSS performs remarkably well against the NMRH33 benchmark set (mean absolute deviation (MAD), 0.10 ppm; maximum deviation (max), 0.26 ppm) with the smallest MAD of all evaluated functionals. The best-performing double-hybrid density functional (DHDF), revDSD-BLYP (MAD, 0.16 ppm; max, 0.35 ppm), performs similarly to hybrid-GGA methods (e.g., mPW1PW91/6-311G(d) (MAD, 0.15 ppm; max, 0.36 ppm)), but at a considerably higher computational cost. The results indicate that currently available double-hybrid DFT methods offer no benefit over GGA (including hybrid and meta) functionals in the calculation of 1H NMR chemical shifts.

The impact of the exact spatial arrangement of the alkali metal on the electronic properties of 9-carbene-9-borafluorene monoanions is assessed, and a series of [K][9-CAAC-9-borafluorene] complexes (

Two-electron reduction of carbene-supported 9-bromo-9-borafluorenes with excess KC8 , Na, or Li-naphthalenide affords six N-heterocyclic carbene (NHC)- or cyclic(alkyl)(amino) carbene (CAAC)-stabilized borafluorene anions (3-8)-the first isolated and structurally authenticated examples of the elusive 9-carbene-9-borafluorene monoanion. The electronic structure, bonding, and aromaticity of the boracyclic anions were comprehensively investigated via computational studies. Compounds 5 and 8 react with metal halides via salt elimination to give new B-E (E=Au, Se, Ge)-containing materials (9-12). Upon reaction with diketones, the carbene ligand cleanly dissociates from 5 or 8 to yield new B-O containing spirocycles (13-14) that cannot be easily obtained using "normal" valent borafluorene compounds. Collectively, these results support the notion that carbene-stabilized monoanionic borafluorenes may serve as a new platform for the one-step construction of higher-value boracyclic materials.

A common feature of d- and p-block elements is that they participate in multiple bonding. In contrast, the synthesis of compounds containing homo- or hetero-nuclear multiple bonds involving s-block elements is extremely rare. Herein, we report the synthesis, molecular structure, and computational analysis of a beryllium imido (Be=N) complex (2), which was prepared via oxidation of a molecular Be0 precursor (1) with trimethylsilyl azide Me3 SiN3 (TMS-N3 ). Notably, compound 2 features the shortest known Be=N bond (1.464 A) to date. This represents the first compound with an s-block metal-nitrogen multiple bond. All compounds were characterized experimentally with multi-nuclear NMR spectroscopy (1 H, 13 C, 9 Be) and single-crystal X-ray diffraction studies. The bonding situation was analyzed with density functional theory (DFT) calculations, which supports the existence of π-bonding between beryllium and nitrogen.

This paper reports results from a search for single and multinucleon disappearance from the O16 nucleus in water within the SNO+ detector using all of the available data. These so-called “invisible” decays do not directly deposit energy within the detector but are instead detected through their subsequent nuclear deexcitation and gamma-ray emission. New limits are given for the partial lifetimes: τ(n→inv)>9.0×1029 years, τ(p→inv)>9.6×1029 years, τ(nn→inv)>1.5×1028 years, τ(np→inv)>6.0×1028 years, and τ(pp→inv)>1.1×1029 years at 90% Bayesian credibility level (with a prior uniform in rate). All but the (nn→inv) results improve on existing limits by a factor of about 3.

It has been previously proposed that pyridines can activate PhICl2 by displacing a chloride and forming the [PhI(Pyr)(Cl)]+ cation as a reactive intermediate. Here we show that pyridine does not displace chloride, but rather forms a weak complex with the iodine via halogen bonding along the C-I bond axis. This interaction is interrogated by NMR, structural, charge density, and theoretical investigations, which all indicate that pyridine does not activate PhICl2 as proposed.

A study on the potential activating role of pyridine in the electrophilic chlorination of anisole by PhICl2 has led to the discovery that soluble sources of chloride ions activate PhICl2 in the reaction at catalytic loadings, greatly increasing the rate of chlorination. It is further shown that presence of chloride increases the rate of decomposition of PhICl2 into PhI and Cl2. The specific mechanism by which chloride induces electrophilic chlorination and decomposition of PhICl2 remains an open question.

The mono- and dianions of CO2 (i.e., CO2− and CO22−) have been studied for decades as both fundamentally important oxycarbanions (anions containing only C and O atoms) and as critical species in CO2 reduction and fixation chemistry. However, CO2 anions are highly unstable and difficult to study. As such, examples of stable compounds containing these ions are extremely limited; the unadulterated alkali salts of CO2 (i.e., MCO2, M2CO2, M = alkali metal) decompose rapidly above 15 K, for example. Herein we report the chemical reduction of a cyclic (alkyl)(amino) carbene (CAAC) adduct of CO2 at room temperature by alkali metals, which results in the formation of CAAC-stabilized alkali CO2− and CO22− clusters. One-electron reduction of CAAC–CO2 adduct (1) with lithium, sodium or potassium metal yields stable monoanionic radicals [M(CAAC–CO2)]n (M = Li, Na, K, 2–4) analogous to the alkali CO2− radical, and two-electron alkali metal reduction affords dianionic clusters of the general formula [M2(CAAC–CO2)]n (5–8) with reduced CO2 units which are structurally analogous to the carbonite anion CO22−. It is notable that crystalline clusters of these alkali–CO2 salts may also be isolated via the “one-pot” reaction of free CO2 with free CAAC followed by the addition of alkali metals – a process which does not occur in the absence of carbene. Each of the products 2–8 was investigated using a combination of experimental and theoretical methods.

ion of a pyridine ligand from Weiss’ reagent ([PhI(Pyr)2]2+) using BF3-Et2O was found to activate Weiss’ reagent towards electrophilic aromatic substitution reactions. The activated species can be isolated when 4-DMAP is used as the pyridine ligand and was determined to be [PhI(4-DMAP)]2+ in solution. The isolated cation was reactive in electrophilic aromatic substitution reactions towards mesitylene, xylene and toluene that Weiss’ reagent itself does not react with.

Borenium ions, originally synthesized as fundamentally important laboratory curiosities, have attracted significant attention due to their applications in catalysis and frustrated Lewis pair chemistry. However, investigations of the materials properties of these types of compounds are exceptionally rare. Herein, we report the synthesis, molecular structures, and optical properties of a new class of air-stable borenium ions, stabilized by the strongly donating carbodicarbene (CDC) ligand (

Borepin, a 7-membered boron-containing heterocycle, has become an emerging molecular platform for the development of new materials and optoelectronics. While electron-deficient borepins are well-established, reduced electron-rich species have remained elusive. Herein we report the first isolable, crystalline borepin radical (2 a, 2 b) and anion (3 a, 3 b) complexes, which have been synthesized by potassium graphite (KC8) reduction of cyclic(alkyl)(amino) carbene-dibenzo[b,d]borepin precursors. Borepin radicals and anions have been characterized by EPR or NMR, elemental analysis, X-ray crystallography, and cyclic voltammetry. In addition, the bonding features have been investigated computationally using density functional theory.

The reactions of boratabenzene and borataphenanthrene anions with group 11 Ph

ion of a pyridine ligand from Weiss' reagent ([PhI(Pyr)

A study on the potential activating role of pyridine in the electrophilic chlorination of anisole by PhICl2 has led to the discovery that soluble sources of chloride ions activate PhICl2 in the reaction at catalytic loadings, greatly increasing the rate of chlorination. It is further shown that presence of chloride increases the rate of decomposition of PhICl2 into PhI and Cl2. The specific mechanism by which chloride induces electrophilic chlorination and decomposition of PhICl2 remains an open question.

The synthesis and reactivity study of the first isolable boraphosphaketene, cyclic(alkyl)(amino) carbene (CAAC)-borafluorene-P=C=O (2), is described. Photolysis of compound 2 results in the formation of CAAC-stabilized BP-doped phenanthryne (3) through tandem decarbonylation, monoatomic phosphide insertion, and ring-expansion. Notably, while BN-doped phenanthryne was previously discussed as a reactive intermediate which could not be isolated, the heavier BP-doped analogue exhibits remarkable solution and solid-state stability. The reactivity of 2 with stable carbenes was also explored. Addition of CAAC to 2 led to migration of the original CAAC ligand from boron to phosphorus and coordination of the added CAAC to carbon, affording compound 4. Reaction of 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (NHC) with 2 resulted in N-C bond activation to give the unusual spiro-heterocyclic compound (5).

A family of four Ir(iii) complexes of the form [Ir(ppy)2(L)]Cl (where ppy = 2-phenyl-pyridine and L = a pyridyl-1,2,4-triazole or pyridyl-1,3,4-oxadiazole ligand bearing a boronic acid group) have been prepared as potential luminescent sensors for carbohydrates. A modular eight step procedure was developed to synthesise the complexes, and this was initiated with the preparation of two benzhydrazide and three S-ethylated pyridine-2-thiocarboxamides precursors. Reaction of these precursors produced three new 1,2,4-triazole- and one 1,3,4-oxadiazole-based ligands substituted with boronic acid pinacol ester groups. The boronic acid pinacol esters were then converted to boronic acids in two steps via potassium trifluoroborate intermediates. The boronic acid substituted ligands and their Ir(iii) complexes were fully characterised using a range of techniques including X-ray crystallography in the case of the pyridyl-1,3,4-oxadiazole ligand and two of the Ir(iii) complexes. The capacity of the synthesised Ir(iii) complexes to form boronic acid cyclic esters with the simple sugars glucose and fructose was evaluated using high-resolution mass spectrometry (HRMS) and photoluminescence titration studies. These studies confirm that the Ir(iii) complexes form adducts with both glucose and fructose, with increased levels of boronic acid cyclic esters being formed with fructose at higher pHs. Theoretical calculations were used to gain insight into the nature of the electronic transitions involved in the electronic absorption and emission spectra.

We report the discovery of a tandem catalytic process to reduce energy demanding substrates, using the [Ir(ppy)2(dtb-bpy)]+ (1+) photocatalyst. The immediate products of photoinitiated electron transfer (PET) between 1+ and triethylamine (TEA) undergo subsequent reactions to generate a previously unknown, highly reducing species (2). Formation of 2 occurs via reduction and semisaturation of the ancillary dtb-bpy ligand, where the TEA radical cation serves as an effective hydrogen atom donor, confirmed by nuclear magnetic resonance, mass spectrometry, and deuterium labeling experiments. Steady-state and time-resolved luminescence and absorption studies reveal that upon irradiation, 2 undergoes electron transfer or proton-coupled electron transfer (PCET) with a representative acceptor (N-(diphenylmethylene)-1-phenylmethanamine; S). Turnover of this new photocatalytic cycle occurs along with the reformation of 1+. We rationalize our observations by proposing the first example of a mechanistic pathway where two distinct yet interconnected photoredox cycles provide access to an extended reduction potential window capable of engaging a wide range of energy demanding and synthetically relevant organic substrates including aryl halides.

The first examples of N-heterocyclic carbene (NHC) and cyclic(alkyl)(amino) carbene (CAAC) stabilized borepinium and borafluorenium heterocycles are reported herein. The optical properties of the heterocyclic borenium cations were tuned by varying the Lewis base and by changing the number of atoms in the ring. More importantly, functionalizing the cationic boron ring system in the NHC-borafluorenium cation affords a temperature-sensitive molecule with reversible colorimetric "turn off/turn on" properties in solution. Notably, this is the first report of thermochromism in these cationic species. This property, which is mediated by an intermolecular boron-oxygen bond equilibrium, was examined in detail by X-ray crystallography, variable temperature-UV/Vis absorption spectroscopy (VT-UV/Vis), and density functional theory (DFT).

Recent synthetic efforts have uncovered several bond activation pathways mediated by beryllium. Having the highest charge density and electronegativity, the chemistry of beryllium often diverges from that of its heavier alkaline earth metal congeners. Herein, we report the synthesis of a new carbodicarbene beryllacycle (2). Compound 2 converts to 3 via an unprecedented cyclic(alkyl)(amino) carbene (CAAC)-promoted ring expansion reaction (RER). While CAAC activates a carbon-beryllium bond, N-heterocyclic carbene (NHC) coordinates to beryllium to give the tetracoordinate complex 4, which contains the longest carbeneC-Be bond to date at 1.856(4) A. All of the compounds were fully characterized by X-ray crystallography, Fourier transform infrared spectroscopy, and 1H, 13C, and 9Be NMR spectroscopy. The ring expansion mechanism was modeled with both NHC and CAAC using density functional theory calculations. While the activation energy for the observed beryllium ring expansion with CAAC was found to be 14 kJ mol-1, the energy barrier for the hypothetical NHC RER is significantly higher (199.1 kJ mol-1).

In the past two decades, the organometallic chemistry of the alkaline earth elements has experienced a renaissance due in part to developments in ligand stabilization strategies. In order to expand the scope of redox chemistry known for magnesium and beryllium, we have synthesized a set of reduced magnesium and beryllium complexes and compared their resulting structural and electronic properties. The carbene-coordinated alkaline earth-halides, (Et2CAAC)MgBr2 (1), (SIPr)MgBr2 (2), (Et2CAAC)BeCl2 (3), and (SIPr)BeCl2 (4) [Et2CAAC = diethyl cyclic(alkyl)(amino) carbene; SIPr = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazole-2-ylidene] were combined with an α-diimine [2,2-bipyridine (bpy) or bis(2,6-diisopropylphenyl)-1,4-diazabutadiene (DippDAB)] and the appropriate stoichiometric amount of potassium graphite to form singly- and doubly-reduced compounds (Et2CAAC)MgBr(DippDAB) (5), (Et2CAAC)MgBr(bpy) (6), (Et2CAAC)Mg(DippDAB) (7), (Et2CAAC)Be(bpy) (8), and (SIPr)Be(bpy) (9). The doubly-reduced compounds 7-9 exhibit substantial π-bonding interactions across the diimine core, metal center, and π-acidic carbene. Each complex was fully characterized by UV-vis, FT-IR, X-ray crystallography, 1H, 13C, and 9Be NMR, or EPR where applicable. We use these compounds to highlight the differences in the organometallic chemistry of the lightest alkaline earth metals, magnesium and beryllium, in an otherwise identical chemical environment.

The mono- and dianions of CO2 (i.e., CO2− and CO22−) have been studied for decades as both fundamentally important oxycarbanions (anions containing only C and O atoms) and as critical species in CO2 reduction and fixation chemistry. However, CO2 anions are highly unstable and difficult to study. As such, examples of stable compounds containing these ions are extremely limited; the unadulterated alkali salts of CO2 (i.e., MCO2, M2CO2, M = alkali metal) decompose rapidly above 15 K, for example. Herein we report the chemical reduction of a cyclic (alkyl)(amino) carbene (CAAC) adduct of CO2 at room temperature by alkali metals, which results in the formation of CAAC-stabilized alkali CO2− and CO22− clusters. One-electron reduction of CAAC–CO2 adduct (1) with lithium, sodium or potassium metal yields stable monoanionic radicals [M(CAAC–CO2)]n (M = Li, Na, K, 2–4) analogous to the alkali CO2− radical, and two-electron alkali metal reduction affords dianionic clusters of the general formula [M2(CAAC–CO2)]n (5–8) with reduced CO2 units which are structurally analogous to the carbonite anion CO22−. It is notable that crystalline clusters of these alkali–CO2 salts may also be isolated via the “one-pot” reaction of free CO2 with free CAAC followed by the addition of alkali metals – a process which does not occur in the absence of carbene. Each of the products 2–8 was investigated using a combination of experimental and theoretical methods., The direct chemical reduction of CAACCO2 adducts by alkali metals to yield multinuclear clusters is reported. The mono- and dianions of CO2 have been studied for decades and are fundamentally important oxycarbanions and critical species in CO2 fixation chemistry.

It has been previously proposed that pyridines can activate PhICl2 by displacing a chloride and forming the [PhI(Pyr)(Cl)]+ cation as a reactive intermediate. Here we show that pyridine does not displace chloride, but rather forms a weak complex with the iodine via halogen bonding along the C-I bond axis. This interaction is interrogated by NMR, structural, charge density, and theoretical investigations, which all indicate that pyridine does not activate PhICl2 as proposed.

The attempted synthesis of N-heterocyclic carbene (NHC)-stabilised dicarbon (C2) fragments via nucleophilic substitution at 1,2-diiodoethane is reported. Rather than the expected SN2 pathway, clean elimination of ethene and formation of an iodoimidazolium cation was observed. The resistance towards nucleophilic substitution piqued interest, and subsequent investigation determined NHC-halogen bonding as the source. This is in contrast to reactions between NHCs and other alkyl halides, where substitution or elimination pathways are reported. A detailed theoretical study between these cases highlights the importance of iodine as a halogen bond donor compared with other halogens, and shows that NHCs are excellent halogen bond acceptors. This reactivity suggests potential for application of the halogen bonding interaction between NHCs and organic compounds.

The reduction of the relatively inert carbon–oxygen bonds of CO2 to access useful CO2-derived organic products is one of the most important fundamental challenges in synthetic chemistry. Facilitating this bond-cleavage using earth-abundant, non-toxic main group elements (MGEs) is especially arduous because of the difficulty in achieving strong inner-sphere interactions between CO2 and the MGE. Herein we report the first successful chemical reduction of CO2 at room temperature by alkali metals, promoted by a cyclic(alkyl)(amino) carbene (CAAC). One-electron reduction of CAAC-CO2 adduct (1) with lithium, sodium or potassium metal yields stable monoanionic radicals clusters [M(CAAC–CO2)]n(M = Li, Na, K, 2-4) and two-electron alkali metal reduction affords open-shell, dianionic clusters of the general formula [M2(CAAC–CO2)]n (5-8). It is notable that these crystalline clusters of reduced CO2 may also be isolated via the “one-pot” reaction of free CO2 with free CAAC followed by the addition of alkali metals – a reductive process which does not occur in the absence of carbene. Each of the products 2-8 were investigated using a combination of experimental and theoretical methods.

The reduction of the relatively inert carbon–oxygen bonds of CO2to access useful CO2-derived organic products is one of the most important fundamental challenges in synthetic chemistry. Achieving this reduction using earth-abundant main group elements (MGEs) is especially arduous because of the difficulty in achieving strong inner-sphere reactions and bond activation events between CO2and the MGE. Herein we report the first successful chemical reduction of a zwitterionic carbene-CO2adduct by either one or two equivalents of light alkali metals to form isolable, room-temperature-stable crystalline clusters exhibiting remarkably diverse electronic and structural characteristics. The reduction of a CAAC-CO2adduct [CAAC–CO2, 1, CAAC = cyclic (alkyl)(amino) carbene] with one equivalent of lithium, sodium or potassium metal yields the monoanionic radicals (THF)3Li2(CAAC–CO2)2(2), (THF)4Na4(CAAC–CO2)4(3), or (THF)4K4(CAAC–CO2)4(4). The reduction of 1by two or more equivalents of lithium, sodium, or potassium yields the open-shell, dianionic clusters (THF)2Li6(CAAC–CO2)3(5), Li12(CAAC–CO2)6(6), Na12(CAAC–CO2)6(7), and K10(CAAC–CO2)5(8). Each of the clusters was studied by a combination of X-ray crystallography, FTIR, UV-Vis, EPR and NMR spectroscopies, and theoretical calculations. The synthetic transformation described in this report results in the facile net reduction of CO2at room temperature by lithium, sodium, and potassium metal without the need for additional metallic promoters, catalysts, or reagents – a process which does not occur in the absence of carbene.

A new strategy to create iridium(iii)-based ECL labels reveals limitations of conventional approaches., Translation of the highly promising electrogenerated chemiluminescence (ECL) properties of Ir(iii) complexes (with tri-n-propylamine (TPrA) as a co-reactant) into a new generation of ECL labels for ligand binding assays necessitates the introduction of functionality suitable for bioconjugation. Modification of the ligands, however, can affect not only the photophysical and electrochemical properties of the complex, but also the reaction pathways available to generate light. Through a combined theoretical and experimental study, we reveal the limitations of conventional approaches to the design of electrochemiluminophores and introduce a new class of ECL label, [Ir(C^N)2(pt-TOxT-Sq)]+ (where C^N is a range of possible cyclometalating ligands, and pt-TOxT-Sq is a pyridyltriazole ligand with trioxatridecane chain and squarate amide ethyl ester), which outperformed commercial Ir(iii) complex labels in two commonly used assay formats. Predicted limits on the redox potentials and emission wavelengths of Ir(iii) complexes capable of generating ECL via the dominant pathway applicable in microbead supported ECL assays were experimentally verified by measuring the ECL intensities of the parent luminophores at different applied potentials, and comparing the ECL responses for the corresponding labels under assay conditions. This study provides a framework to tailor ECL labels for specific assay conditions and a fundamental understanding of the ECL pathways that will underpin exploration of new luminophores and co-reactants.

The 9-borataphenanthrene anion is easily accessed by deprotonation of a 9,10-dihydro-9-boraphenanthrene and its diverse reactivity is investigated. Alkylation occurs at the carbon atom adjacent to boron, and room temperature hydroboration occurs across the B=C bond. The π-manifold of the central BC5 ring coordinates to chromium in an η6 fashion while only the B=C unit binds η2 to gold, indicating versatility of the 9-borataphenanthrene anion as a ligand. Supporting calculations rationalize the reactivity and aromaticity is corroborated by nucleus-independent chemical shift (NICS) indices.

The reactions of a monomeric borole and a dimeric borole with 2,3-dimethyl-1,3-butadiene and 1,3-cyclohexadiene were investigated. The monomeric borole reacted at ambient temperature whereas heat was required to crack the dimer to form the monomer and induce reactivity. 2,3-Dimethyl-1,3-butadiene reacts to give diverse products resulting from a cycloaddition process with the B-C moiety of the boroles acting as a dienophile, followed by rearrangements to furnish bicyclic species. For 1,3-cyclohexadiene, a [4+2] process is observed in which 1,3-cyclohexadiene serves as the dienophile and the boroles as the diene partner. The experimental results are corroborated with mechanistic theoretical calculations that indicate boroles can serve as either a diene or dienophile in cycloaddition reactions with dienes.

The endocyclic ring expansion of N-heterocyclic carbene (NHC) rings containing one N atom and one P, N, C, O or S heteroatom has been investigated in a computational study. Ring expansion was determined to follow a common pathway, leading to a final expanded six-membered ring that was predicted to be thermodynamically stable for all heterocycles. However, reactivity is driven by kinetics with ring-expansion reactivity not expected for the P/NHC and C/NHC (cAAC) containing heterocycles due to large barriers for ring-expansion. In contrast, ring expansion is predicted to be feasible for N-heterocyclic carbenes containing an O (O/NHC) or S (S/NHC) heteroatom, with insertion into the O-C and S-C bond favoured over insertion into the N-C bond, respectively.