Conjugated polymers based on metalla-aromatic building blocks.

Conjugated polymers usually require strategies to expand the range of wavelengths absorbed and increase solubility. Developing effective strategies to enhance both properties remains challenging. Herein, we report syntheses of conjugated polymers based on a family of metalla-aromatic building blocks via a polymerization method involving consecutive carbyne shuttling processes. The involvement of metal d orbitals in aromatic systems efficiently reduces band gaps and enriches the electron transition pathways of the chromogenic repeat unit. These enable metalla-aromatic conjugated polymers to exhibit broad and strong ultraviolet-visible (UV-Vis) absorption bands. Bulky ligands on the metal suppress π-π stacking of polymer chains and thus increase solubility. These conjugated polymers show robust stability toward light, heat, water, and air. Kinetic studies using NMR experiments and UV-Vis spectroscopy, coupled with the isolation of well-defined model oligomers, revealed the polymerization mechanism.

Recent advances in the chemistry of isolable carbene analogues with group 13-15 elements.

Carbenes (R2C:), compounds with a divalent carbon atom containing only six valence shell electrons, have evolved into a broader class with the replacement of the carbene carbon or the RC moiety with main group elements, leading to the creation of main group carbene analogues. These analogues, mirroring the electronic structure of carbenes (a lone pair of electrons and an empty orbital), demonstrate unique reactivity. Over the last three decades, this area has seen substantial advancements, paralleling the innovations in carbene chemistry. Recent studies have revealed a spectrum of unique carbene analogues, such as monocoordinate aluminylenes, nitrenes, and bismuthinidenes, notable for their extraordinary properties and diverse reactivity, offering promising applications in small molecule activation. This review delves into the isolable main group carbene analogues that are in the forefront from 2010 and beyond, spanning elements from group 13 (B, Al, Ga, In, and Tl), group 14 (Si, Ge, Sn, and Pb) and group 15 (N, P, As, Sb, and Bi). Specifically, this review focuses on the potential amphiphilic species that possess both lone pairs of electrons and vacant orbitals. We detail their comprehensive synthesis and stabilization strategies, outlining the reactivity arising from their distinct structural characteristics.

Correction: Recent advances in the chemistry of isolable carbene analogues with group 13-15 elements.

Correction for 'Recent advances in the chemistry of isolable carbene analogues with group 13-15 elements' by Mian He et al., Chem. Soc. Rev., 2024, https://doi.org/10.1039/D3CS00784G.

Carbene-Stabilized Phosphagermylenylidene: A Heavier Analog of Isonitrile.

Phosphagermylenylidenes (R-P═Ge), as heavier analogs of isonitriles, whether in their free state or as complexes with a Lewis base, have not been previously identified as isolable entities. In this study, we report the synthesis of a stable monomeric phosphagermylenylidene within the coordination sphere of a Lewis base under ambient conditions. This species was synthesized by Lewis base-induced dedimerization of a cyclic phosphagermylenylidene dimer or via Me3SiCl elimination from a phosphinochlorogermylene framework. The deliberate integration of a bulky, electropositive N-heterocyclic boryl group at the phosphorus site, combined with coordination stabilization by a cyclic (alkyl)(amino)carbene at the low-valent germanium site, effectively mitigated its natural tendency toward oligomerization. Structural analyses and theoretical calculations have demonstrated that this unprecedented species features a P═Ge double bond, characterized by conventional electron-sharing π and σ bonds, complemented by lone pairs at both the phosphorus and germanium atoms. Preliminary reactivity studies show that this base-stabilized phosphagermylenylidene demonstrates facile release of ligands at the Ge atom, coordination to silver through the lone pair on P, and versatile reactivity including both (cyclo)addition and cleavage of the P═Ge double bond.

Colorectal polyps in young adults: a retrospective review of colonoscopy data from Toowoomba and the Darling Downs.

BACKGROUND: Polyps are the predominant precursors of colorectal cancer. In the past three decades, the incidence and mortality rates of colorectal cancer have been increasing in adults younger than 50 years. AIMS: The aim of this clinical audit was to evaluate the prevalence, characteristics and clinical associations of polyps in adults aged 18-49 years presenting to an established private gastroenterology clinic in the Toowoomba Darling Downs region. METHODS: The audit included data from 353 patient records held by the Toowoomba Gastroenterology Clinic. Data extracted from patient medical records through the Medical Director program software contained structured endoscopy/colonoscopy and histology reports of excised lesions of patients presenting to the clinic. The extract involved identifying all patients aged 18-49 years in the database from January 2019 to March 2022. Patients were screened based on audit inclusion and exclusion criteria. Patients were risk stratified for recommended surveillance intervals as per Australian Clinical Guidelines. RESULTS: Of the sample population, 33.4% were identified with polyps and 22.4% were identified with neoplastic polyps (NPs). A total of 6.7% of 18- to 29-year-old patients were identified with intermediate risk for colorectal cancer (CRC) screening, and 19.8% and 19.3% of 30- to 39-year-old and 40- to 49-year-old patients identified with intermediate or high risk for CRC screening respectively. Increased age, greater size of polyps and surveillance of previous polyps were associated with increased NP prevalence. CONCLUSIONS: Data from this audit supported the temporal trend of increasing prevalence of polyps in adults younger than 50 years. Patient cohorts aged 30-39 and 40-49 years may benefit from earlier first colonoscopies. Findings could be the impetus for future research in young adults presenting for colonoscopy.

Selective Hydroboration of C-C Single Bonds without Transition-metal Catalysis.

Selective hydroboration of C-C single bonds presents a fundamental challenge in the chemical industry. Previously, only catalytic systems utilizing precious metals Ir and Rh, in conjunction with N- and P- ligands, could achieve this, ensuring bond cleavage and selectivity. In sharp contrast, we discovered an unprecedented and general transition-metal-free system for the hydroboration of C-C single bonds. This methodology is transition-metal and ligand-free and surpasses the transition-metal systems regarding chemo- and regioselectivities, substrate versatility, or yields. In addition, our system tolerates various functional groups such as Ar-X (X = halides), heterocyclic rings, ketones, esters, amides, nitro, nitriles, and C=C double bonds, which are typically susceptible to hydroboration in the presence of transition metals. As a result, a diverse range of γ-boronated amines with varied structures and functions has been readily obtained. Experimental mechanistic studies, density functional theory (DFT), and intrinsic bond orbital (IBO) calculations unveiled a hydroborane-promoted C-C bond cleavage and hydride-shift reaction pathway. The carbonyl group of the amide suppresses dehydrogenation between the free N-H and hydroborane. The lone pair on the nitrogen of the amide facilitates the cleavage of C-C bonds in cyclopropanes.

Aromatic 1,4,2,3-Diazadiborole Featuring an Unsymmetrical B=B Entity: A Versatile Synthon for Unusual Boron Heterocycles.

The replacement of a CC unit with an isoelectronic BN unit in aromatic systems can give rise to molecules and materials with fascinating properties. We report here the synthesis, characterization, and reactivity of a 1,4,2,3-diazadiborole species, 2, featuring an unprecedented 6π-aromatic BN-heterocyclic moiety that is isoelectronic to cyclopentadienide (Cp-). Bearing an unsymmetrical B=B entity, 2 exhibits reactivity toward oxidants, protic reagents, electrophiles, and unsaturated substrates. This reactivity facilitates the synthesis of a variety of novel mono- and bicyclic organoboron derivatives through mechanisms including ring retention, cleavage/recombination, annulation, and expansion. These findings reveal innovative synthetic routes to BN-embedded aromatic compounds via desymmetrization, affording unique building blocks for synthetic chemistry.

Crystalline Neutral Aluminum Selenide/Telluride: Isoelectronic Aluminum Analogues of Carbonyls.

Neutral aluminum chalcogenides (R-Al(L)═Ch; L = ligand, Ch = chalcogen), stabilized by a Lewis base ligand, represent isoelectronic counterparts to carbonyl compounds and have long been pursued for isolation. Herein, we present the synthesis of an aluminum selenide, [N]-Al(iPr2-bimy)═Se, and an aluminum telluride, [N]-Al(iPr2-bimy)═Te, under ambient conditions ([N] = 1,8-bis(3,5-di-tert-butylphenyl)-3,6-di-tert-butylcarbazolyl; iPr2-bimy = 1,3-diisoproplylbenzimidazole-2-ylidene). These compounds arise from the oxidation reaction of [N]-Al(iPr2-bimy) with Se and (nBu)3P═Te, respectively. One notable characteristic of the Al and Ch interaction is the presence of an Al-Ch σ bond, strengthened by the electrostatic attraction between the Al+ and Ch- centers as well as the donation of lone pairs from Ch into vacant orbitals at Al. This results in an Al-Ch multiple bond with an ambiphilic nature. Preliminary investigations into their reactivity unveil their remarkable propensity for facile (cyclo)addition reactions with diverse substrates, including PhCCH, PhCN, AdN3, MeI, PhSiH3, and C6F6, leading to the formation of unprecedented main group heterocycles and alumachalcogenides.

Si-B Functional Group Exchange Reaction Enabled by a Catalytic Amount of BH3: Scope, Mechanism, and Application.

Functional group exchanges based on single-bond transformation are rare and challenging. In this regard, functional group exchange reactions of hydrosilanes proved to be more problematic. This is because this exchange requires the cleavage of the C-Si bond, while the Si-H bond is relatively easily activated for hydrosilanes. Herein, we report the first Si-B functional group exchange reactions of hydrosilanes with hydroboranes simply enabled by BH3 as a catalyst. Our methodology works for various aryl and alkyl hydrosilanes and different hydroboranes with the tolerance of general functional groups (up to 115 examples). Control experiments and density functional theory (DFT) studies reveal a distinct reaction pathway that involves consecutive C-Si/B-H and C-B/B-H σ-bond metathesis. Further investigations of using more readily available chlorosilanes, siloxane, fluorosilane, and silylborane for Si-B functional group exchanges, Ge-B functional group exchanges, and depolymerizative Si-B exchanges of polysilanes are also demonstrated. Moreover, the regeneration of MeSiH3 from polymethylhydrosiloxane (PMHS) is achieved. Notably, the formal hydrosilylation of a wide range of alkenes with SiH4 and MeSiH3 to selectively produce (chiral)trihydrosilanes and (methyl)dihydrosilanes is realized using inexpensive and readily available PhSiH3 and PhSiH2Me as gaseous SiH4 and MeSiH3 surrogates.

BN Analogue of Butadiyne: A Platform for Dinitrogen Release and Reduction.

Exploration of the metallomimetic chemistry of main group elements is of the utmost importance from the perspective of both fundamental research and potential applications. Here, we report the synthesis, bonding analysis, and reactivities of an isolable diiminoborane, Mes*B≡N─N≡BMes* (Mes* = 2,4,6-tri-tert-butylphenyl) (1), a BN analogue of butadiyne. This species is characterized by a conjugated B≡N─N≡B moiety, a structural feature that enables the controlled release of N2 when it is exposed to organic nitriles. Furthermore, the N2 unit in 1 could be reduced to an ammonium salt via cleavage of the BN triple bond. Our work shows a rare example of an unsaturated BN system, serving as a platform for both the release and reduction of N2. This discovery opens new pathways and holds substantial influence on the future design of functional main group N2 species.

Alkoxyphosphorane/Borane Cooperative Alkylations: A Frustrated Lewis Pair Version of the Mitsunobu Reaction.

The combination of the alkoxyphosphoranes, Ph2 P(OR)(O2 C6 Cl4 ) and the borane B(C6 F5 )3 generates the zwitterions 3 which act as FLP to effect the alkylation of several nucleophiles affording C-C, C-N, C-H and C-Cl coupling products. A DFT study shows the reaction proceeds via an FLP activation pathway generating an alkoxyphosphonium intermediate which effects the alkylation of the nucleophiles, akin to the Mitsunobu reaction.

Utilization of a Tris(carbene)borate Ligand for Umpolung Reactivity of a Nucleophilic Tin(II) Cation Salt.

We show that a tris(carbene)borate (TCB) ligand, namely [PhB(tBuIm)3]- ([PhB(tBuIm)3]- = phenyltris(3-tert-butylimidazol-2-ylidene)borato), is capable of stabilizing an unprecedented nucleophilic Sn(II) cation salt. Unlike known Sn(II) cations, the strong electron-donating ability of [PhB(tBuIm)3]- makes the cationic tin atom electron-rich, σ-donating yet slightly π-accepting, which allows for the ensuing facile oxidation with o-chloranil and S8 as well as coordination with coinage metals. The former oxidations give the Sn(IV) cation salts, while the latter reactions produce the metal complexes. The electronic structures of these species are thoroughly probed by quantum chemical computations. These results uncover an added role for TCB ligands in isolating unprecedented p-block species.

Derivatization of an Alkylideneborane with B═C Bond Cleavage.

We present the synthesis, structural characterization, and reactivity of alkylideneborane 2, supported by π-donating N-heterocyclic imino and σ-donating N-heterocyclic carbene (NHC) ligands. The incorporation of these ligands effectively weakens the B═C bond strength, leading to enhanced reactivity. Consequently, selective cleavage of the B═C bond can be achieved using pyridine-N-oxide, sulfur, and selenium, resulting in the formation of 1,3-dioxa-2,4-diboretane 3, thioxoborane 4, and selenoborane 5, respectively. Furthermore, intriguing B═C bond insertions with CO2 and CS2 are observed, affording zwitterionic borenium/fluorenide 6 and dithiaboretane 7. The former species 6 is readily converted to transient oxoborane and imidazolium enolate, showcasing the bora-Wittig reaction of alkylideneborane. This investigation highlights the potential of alkylideneborane as a versatile building block for synthesizing novel organoboron compounds through unconventional transformations.

Stable Ketenyl Anions via Ligand Exchange at an Anionic Carbon as Powerful Synthons.

Under an atmosphere of carbon monoxide (CO), a (phosphino)diazomethyl anion salt [[P]-CN2 ][K(18-C-6)(THF)] (1) ([P]=[(CH2 )(NDipp)]2 P; 18-C-6=18-crown-6; Dipp=2,6-diisopropylphenyl) undergoes a facile N2 /CO exchange reaction giving the (phosphino)ketenyl anion salt [[P]-CCO][K(18-C-6)] (2). Oxidation of 2 with elemental Se affords the (selenophosphoryl)ketenyl anion salt [P](Se)-CCO][K(18-C-6)] (3). These ketenyl anions feature a strongly bent geometry at the P-bound carbon and this carbon atom is highly nucleophilic. The electronic structure of the ketenyl anion [[P]-CCO]- of 2 is examined by theoretical studies. Reactivity investigations demonstrate 2 as a versatile synthon for derivatives of ketene, enolate, acrylate and acrylimidate moieties.

An Isolable Radical Anion Featuring a 2-Center-3-Electron π-Bond without a Clearly Defined σ-Bond.

Featuring an extra electron in the π* antibonding orbital, species with a 2-center-3-electron (2c3e) π bond without an underlying σ bond are scarcely known. Herein, we report the synthesis, isolation and characterization of a radical anion salt [K(18-C-6)]+ {[(HCNDipp)2 Si]2 P2 }⋅- (i.e. [K(18-C-6)]+ 3⋅- ) (18-C-6=18-crown-6, Dipp=2,6-diisopropylphenyl), in which 3⋅- features a perfectly planar Si2 P2 four-membered ring. This species represents the first example of a Si- and P-containing analog of a bicyclo[1.1.0]butane radical anion. The unusual bonding motif of 3⋅- was thoroughly investigated via X-ray diffraction crystallography, electron paramagnetic resonance spectroscopy (EPR), and calculations by density functional theory (DFT), which collectively unveiled the existence of a 2c3e π bond between the bridgehead P atoms and no clearly defined supporting P-P σ bond.

Geometrically Constrained Organoboron Species as Lewis Superacids and Organic Superbases.

This report unveils an advancement in the formation of a Lewis superacid (LSA) and an organic superbase by the geometrical deformation of an organoboron species towards a T-shaped geometry. The boron dication [2]2+ supported by an amido diphosphine pincer ligand features both a large fluoride ion affinity (FIA>SbF5 ) and hydride ion affinity (HIA>B(C6 F5 )3 ), which qualifies it as both a hard and soft LSA. The unusual Lewis acidic properties of [2]2+ are further showcased by its ability to abstract hydride and fluoride from Et3 SiH and AgSbF6 respectively, and effectively catalyze the hydrodefluorination, defluorination/arylation, as well as reduction of carbonyl compounds. One and two-electron reduction of [2]2+ affords stable boron radical cation [2]⋅+ and borylene 2, respectively. The former species has an extremely high spin density of 0.798e at the boron atom, whereas the latter compound has been demonstrated to be a strong organic base (calcd. pKBH + (MeCN)=47.4) by both theoretical and experimental assessment. Overall, these results demonstrate the strong ability of geometric constraining to empower the central boron atom.

Facile Synthesis of the Dicyanophosphide Anion via Electrochemical Activation of White Phosphorus: An Avenue to Organophosphorus Compounds.

Organophosphorus compounds (OPCs) have gained tremendous interest in the past decades due to their wide applications ranging from synthetic chemistry to materials and biological sciences. We describe herein a practical and versatile approach for the transformation of white phosphorus (P4) into useful OPCs with high P atom economy via a key bridging anion [P(CN)2]-. This anion can be prepared on a gram scale directly from P4 through an electrochemical process. A variety of OPCs involving phosphinidenes, cyclophosphanes, and phospholides have been made readily accessible from P4 in a two-step manner. Our approach has a significant impact on the future preparation of OPCs in laboratory and industrial settings.

A Free Phosphaborene Stable at Room Temperature.

Free phosphaborenes (R-P═B-R) are PB analogues of alkynes, and their isolation is a long-sought-after goal. Herein, we demonstrate that the combination of a π-donating and a π-accepting substituent with bulky flanking arene rings enables the isolation of a crystalline free phosphaborene 5 at room temperature. This electron push-pull cooperation, combined with the kinetic protection, hinders its inherent tendency to oligomerize. This species features a PB double bond consisting of a conventional σ bond and a delocalized π bond. The lone pair of electrons at P slightly contributes to the PB bonding. Preliminary reactivity studies show that 5 undergoes facile (cyclo)addition reactions with p-methyl benzaldehyde, p-fluoroacetophenone, and carbon disulfide, the last of which results in facile PB double bond cleavage. Our strategy has a significant impact on the future synthesis of ambiphilic heterodiatomic multiply bonded main group species.

Selection of M2+ -Independent RNA-Cleaving DNAzymes with Side-Chains Mimicking Arginine and Lysine.

Sequence-specific cleavage of RNA by nucleic acid catalysts in the absence of a divalent metal cation (M2+ ) has remained an important goal in biomimicry with potential therapeutic applications. Given the lack of functional group diversity in canonical nucleotides, modified nucleotides with amino acid-like side chains were used to enhance self-cleavage rates at a single embedded ribonucleoside site. Previous works relied on three functional groups: an amine, a guanidine and an imidazole ensconced on three different nucleosides. However, to date, few studies have systematically addressed the necessity of all three modifications, as the value of any single modified nucleoside is contextualized at the outset of selection. Herein, we report on the use of only two modified dNTPs, excluding an imidazole, i. e. 5-(3-guanidinoallyl)-2'-dUTP (dUga TP) and 5-aminoallyl-2'-dCTP (dCaa TP), to select in-vitro self-cleaving DNAzymes that cleave in the absence of M2+ in a pH-independent fashion. Cleavage shows biphasic kinetics with rate constants that are significantly higher than in unmodified DNAzymes and compare favorably to certain DNAzymes involving an imidazole.

Surfing motility is a complex adaptation dependent on the stringent stress response in Pseudomonas aeruginosa LESB58.

Cystic fibrosis (CF) is a genetic disease that affects mucin-producing body organs such as the lungs. Characteristic of CF is the production of thick, viscous mucus, containing the glycoprotein mucin, that can lead to progressive airway obstruction. Recently, we demonstrated that the presence of mucin induced a rapid surface adaptation in motile bacteria termed surfing motility, which data presented here indicates is very different from swarming motility. Pseudomonas aeruginosa, the main colonizing pathogen in CF, employs several stress coping mechanisms to survive the highly viscous environment of the CF lung. We used motility-based assays and RNA-Seq to study the stringent stress response in the hypervirulent CF isolate LESB58 (Liverpool Epidemic Strain). Motility experiments revealed that an LESB58 stringent response mutant (ΔrelAΔspoT) was unable to surf. Transcriptional profiling of ΔrelAΔspoT mutant cells from surfing agar plates, when compared to wild-type cells from the surfing edge, revealed 2,584 dysregulated genes. Gene Ontology and KEGG enrichment analysis revealed effects of the stringent response on amino acid, nucleic acid and fatty acid metabolism, TCA cycle and glycolysis, type VI secretion, as well as chemotaxis, cell communication, iron transport, nitrogen metabolic processes and cyclic-di-GMP signalling. Screening of the ordered PA14 transposon library revealed 224 mutants unable to surf and very limited overlap with genes required for swarming. Mutants affecting surfing included two downstream effector genes of the stringent stress response, the copper regulator cueR and the quinolone synthase pqsH. Both the cueR and pqsH cloned genes complemented the surfing deficiency of ΔrelAΔspoT. Our study revealed insights into stringent stress dependency in LESB58 and showed that surfing motility is stringently-controlled via the expression of cueR and pqsH. Downstream factors of the stringent stress response are important to investigate in order to fully understand its ability to colonize and persist in the CF lung.