Mechanistic Studies on the Bismuth-Catalyzed Transfer Hydrogenation of Azoarenes.

Organobismuth-catalyzed transfer hydrogenation has recently been disclosed as an example of low-valent Bi redox catalysis. However, its mechanistic details have remained speculative. Herein, we report experimental and computational studies that provide mechanistic insights into a Bi-catalyzed transfer hydrogenation of azoarenes using p-trifluoromethylphenol (4) and pinacolborane (5) as hydrogen sources.

Cooperation towards nobility: equipping first-row transition metals with an aluminium sword.

The exploration for noble metals substitutes in catalysis has become a highly active area of research, driven by the pursuit of sustainable chemical processes. Although the utilization of base metals holds great potential as an alternative, their successful implementation in predictable catalytic processes necessitates the development of appropriate ligands. Such ligands must be capable of controlling their intricate redox chemistry and promote two-electron events, thus mimicking well-established organometallic processes in noble metal catalysis.

C-H Amination Reactions Mediated by Metastable Pseudo- Masked Aryl-Co-nitrene Species.

Cobalt-catalyzed C-H amination via M-nitrenoid species is spiking the interest of the research community. Understanding this process at a molecular level is a challenging task, and here we report a well-defined macrocyclic system featuring a pseudo- aryl-Co species that reacts with aliphatic azides to effect intramolecular C-N bond formation. Strikingly, a putative aryl-Co═NR nitrenoid intermediate species is formed and is rapidly trapped by a carboxylate ligand to form a carboxylate masked-nitrene, which functions as a shortcut to stabilize and guide the reaction to productive intramolecular C-N bond formation.

Mechanism of the Aryl-F Bond-Forming Step from Bi(V) Fluorides.

In this article, we describe a combined experimental and theoretical mechanistic investigation of the C(sp)-F bond formation from neutral and cationic high-valent organobismuth(V) fluorides, featuring a dianionic bis-aryl sulfoximine ligand. An exhaustive assessment of the substitution pattern in the ligand, the sulfoximine, and the reactive aryl on neutral triarylbismuth(V) difluorides revealed that formation of dimeric structures in solution promotes facile Ar-F bond formation. Noteworthy, theoretical modeling of reductive elimination from neutral bismuth(V) difluorides agrees with the experimentally determined kinetic and thermodynamic parameters.

Well-Defined Aryl-Fe Complexes in Cross-Coupling and C-H Activation Processes.

Herein we explore the intrinsic organometallic reactivity of iron embedded in a tetradentate NC macrocyclic ligand scaffold that allows the stabilization of aryl-Fe species, which are key intermediates in Fe-catalyzed cross-coupling and C-H functionalization processes. This study covers C-H activation reactions using and FeCl, biaryl C-C coupling product formation through reaction with Grignard reagents, and cross-coupling reactions using or in combination with Fe(CO). Synthesis under light irradiation and moderate heating (50 °C) affords the aryl-Fe complexes [Fe(Br)( )(CO)] ( ) and [Fe( )(CO)]Br ( ).

Smart Dual-Functionalized Gold Nanoclusters for Spatio-Temporally Controlled Delivery of Combined Chemo- and Photodynamic Therapy.

We report the preparation of gold nanoclusters (AuNCs) as a delivery vehicle for the clinically approved photodynamic and chemotherapeutic agents Protoporphyrin IX (PpIX) and doxorubicin (DOX), respectively, and their effect on tumor cells. DOX was attached to the gold nanoclusters through a singlet oxygen-cleavable linker and was therefore released after PpIX irradiation with red light, contributing, synergistically with singlet oxygen, to induce cell death. The doubly functionalized AuNCs proved more effective than a combination of individually functionalized AuNCs.

Bismuth-Catalyzed Oxidative Coupling of Arylboronic Acids with Triflate and Nonaflate Salts.

Herein we present a Bi-catalyzed cross-coupling of arylboronic acids with perfluoroalkyl sulfonate salts based on a Bi(III)/Bi(V) redox cycle. An electron-deficient sulfone ligand proved to be key for the successful implementation of this protocol, which allows the unusual construction of C(sp)-O bonds using commercially available NaOTf and KONf as coupling partners. Preliminary mechanistic studies as well as theoretical investigations reveal the intermediacy of a highly electrophilic Bi(V) species, which rapidly eliminates phenyl triflate.

Unravelling the mechanism of cobalt-catalysed remote C-H nitration of 8-aminoquinolinamides and expansion of substrate scope towards 1-naphthylpicolinamide.

Previously, an unexpected Co-catalysed remote C-H nitration of 8-aminoquinolinamide compounds was developed. This report provided a novel reactivity for Co which was assumed to proceed through the mechanistic pathway already known for analogous Cu-catalysed remote couplings of the same substrates. In order to shed light into this intriguing, and previously unobserved reactivity for Co, a thorough computational study has now been performed, which has allowed for a full understanding of the operative mechanism.

Aerobic C-C and C-O bond formation reactions mediated by high-valent nickel species.

Nickel complexes have been widely employed as catalysts in C-C and C-heteroatom bond formation reactions. While Ni(0), Ni(i), and Ni(ii) intermediates are most relevant in these transformations, recently Ni(iii) and Ni(iv) species have also been proposed to play a role in catalysis. Reported herein is the synthesis, detailed characterization, and reactivity of a series of Ni(ii) and Ni(iii) metallacycle complexes stabilized by tetradentate pyridinophane ligands with various N-substituents.

Fluorination of arylboronic esters enabled by bismuth redox catalysis.

Bismuth catalysis has traditionally relied on the Lewis acidic properties of the element in a fixed oxidation state. In this paper, we report a series of bismuth complexes that can undergo oxidative addition, reductive elimination, and transmetallation in a manner akin to transition metals. Rational ligand optimization featuring a sulfoximine moiety produced an active catalyst for the fluorination of aryl boronic esters through a bismuth (III)/bismuth (V) redox cycle.

Bi(I)-Catalyzed Transfer-Hydrogenation with Ammonia-Borane.

A catalytic transfer-hydrogenation utilizing a well-defined Bi(I) complex as catalyst and ammonia-borane as transfer agent has been developed. This transformation represents a unique example of low-valent pnictogen catalysis cycling between oxidation states I and III, and proved useful for the hydrogenation of azoarenes and the partial reduction of nitroarenes. Interestingly, the bismuthinidene catalyst performs well in the presence of low-valent transition-metal sensitive functional groups and presents orthogonal reactivity compared to analogous phosphorus-based catalysis.

Towards optimized naphthalocyanines as sonochromes for photoacoustic imaging .

In this paper we establish a methodology to predict photoacoustic imaging capabilities from the structure of absorber molecules (sonochromes). The comparative and screening of naphthalocyanines and cyanine dyes has shown a substitution pattern dependent shift in photoacoustic excitation wavelength, with distal substitution producing the preferred maximum around 800 nm. Central ion change showed variable production of photoacoustic signals, as well as singlet oxygen photoproduction and fluorescence with the optimum for photoacoustic imaging being nickel(II).

Carboxylate-Assisted Formation of Aryl-Co(III) Masked-Carbenes in Cobalt-Catalyzed C-H Functionalization with Diazo Esters.

Herein we describe the synthesis of a family of aryl-Co(III)-carboxylate complexes and their reactivity with ethyl diazoacetate. Crystallographic, full spectroscopic characterization, and theoretical evidence of unique C-metalated aryl-Co(III) enolate intermediates is provided, unraveling a carboxylate-assisted formation of aryl-Co(III) masked-carbenes. Moreover, additional evidence for an unprecedented Co(III)-mediated intramolecular S2-type C-C bond formation in which the carboxylate moiety acts as a relay is disclosed.

Acid- and hydrogen-bonding-induced switching between 22-π and 18-π electron conjugations in 2-aminothiazolo[4,5-c]porphycenes.

2-Aminothiazolo[4,5-c]porphycenes are a novel class of 22-π electron aromatic porphycene derivatives prepared by click reaction of porphycene isothiocyanates with primary and secondary amines with high potential as near-infrared theranostic labels. Herein, the optical and photophysical properties of 2-aminothiazolo[4,5-c]porphycenes have been studied, revealing a strong dependence on hydrogen bond donor solvents and acids. High hydrogen bond donor solvents and acids shift the absorption and fluorescence emission of 2-aminothiazolo[4,5-c]porphycenes to the blue due to a contraction of their aromatic system from 22-π to 18-π electrons.

Distance-Dependent Plasmon-Enhanced Singlet Oxygen Production and Emission for Bacterial Inactivation.

Herein, we synthesized a series of 10 core-shell silver-silica nanoparticles with a photosensitizer, Rose Bengal, tethered to their surface. Each nanoparticle possesses an identical silver core of about 67 nm, but presents a different silica shell thickness ranging from 5 to 100 nm. These hybrid plasmonic nanoparticles thus afford a plasmonic nanostructure platform with a source of singlet oxygen ((1)O2) at a well-defined distance from the metallic core.

Synthesis, photophysical characterization, and photoinduced antibacterial activity of methylene blue-loaded amino- and mannose-targeted mesoporous silica nanoparticles.

Over the last 20 years, the number of pathogenic multi-resistant microorganisms has grown steadily, which has stimulated the search for new strategies to combat antimicrobial resistance. Antimicrobial photodynamic therapy (aPDT), also called photodynamic inactivation, is emerging as a promising alternative to treatments based on conventional antibiotics. We have explored the effectiveness of methylene blue-loaded targeted mesoporous silica nanoparticles (MSNP) in the photodynamic inactivation of two Gram negative bacteria, namely Escherichia coli and Pseudomonas aeruginosa.

A novel fluoro-chromogenic click reaction for the labelling of proteins and nanoparticles with near-IR theranostic agents.

Reaction of porphycene isothiocyanates with primary and secondary amines leads to the formation of thiazolo[4,5-c]porphycenes, with a substantial shift in the absorption and fluorescence spectra. The conjugates show fluorescence in the near-infrared and are capable of photosensitizing the production of the cytotoxic species singlet oxygen.

Structural modeling of iron halogenases: synthesis and reactivity of halide-iron(IV)-oxo compounds.

A structural synthetic model of the iron(IV)-oxo-halide active species of non-heme iron dependent halogenases is reported. Compounds with general formula [Fe(IV)(O)(X)(Pytacn)](+) (1-X, X = Cl, Br) have been prepared and characterized spectroscopically and chemically with regard to their oxidizing ability. 1-X performs hydrogen-atom abstraction of C-H bonds at reaction rates 2-3 times faster than the corresponding solvato dicationic species, thus modelling the first step in C-H functionalization taking place in natural halogenation.