Silver Carboxylate Research Articles

Fluoro and Trifluoromethyl Benzoyl Hypoiodite Complexes with Substituted Pyridines.

Based on the prior observation of the trifluoroacetate hypoiodite, CF3C(O)OI, demonstrating the largest σ-hole of a neutral halogen bond donor, a series of mono- and bis-carbonyl hypoiodites utilising trifluoromethyl or fluorine substituents at various positions of a parent benzoyl skeleton have been synthesised. The carbonyl hypoiodite complexes were prepared via cation exchange of the silver(I) cations with iodine(I) from the respective silver(I) carboxylates and dicarboxylates as the synthetic precursors. A range of pyridinic Lewis bases of varying nucleophilicities were used to stabilise the carbonyl hypoiodites to further probe their properties. The silver(I) intermediates with these Lewis bases were also isolated for silver(I) pentafluorobenzoate, providing additional insight into the cation exchange reaction. All complexes were characterised both in solution (1H, 1H-15N HMBC, 19F) and in the solid state (SCXRD), permitting insights into the formation of the elusive pyridine-iodine(I) cation.

Silver carboxylate-TiO2/polydimethyl siloxane is a safe and effective antimicrobial with significant wound care potential.

With the rise in antibiotic resistance, new methodologies are needed to combat musculoskeletal infections. Silver is an antimicrobial that can be synthesized in different forms, but its pharmacokinetics are difficult to control. This study details the antibacterial efficacy and cellular cytotoxicity of a formulation consisting of silver carboxylate (AgCar) released through a titanium dioxide/polydimethylsiloxane matrix with a predictable release profile on Pseudomonas aeruginosa, Acinetobacterium baumannii, and human-derived primary osteoblasts. Through an Institutional Animal Care and Use Committee and IRB-approved protocol, AgCar was applied to live Yucatan porcine skin and histologically analyzed for skin penetration. Graphite Furnace Atomic Absorption Spectroscopy (GFAAS) was used to measure elution of AgCar. Dose-response curves were generated through optical density to assess potency. Finally, 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay was used to quantify the cellular cytotoxicity of the novel formulation. The results were subject to statistical analysis using analysis of variance and post hoc Tukey tests. The silver carboxylate coating demonstrated deep penetration into the epithelium at the level of the deep pilosebaceous glands in animal models. GFAAS testing demonstrated the extended elution profile of silver carboxylate over 96 hours, while 100% silver with no titanium dioxide-polydimethylsiloxane matrix fully eluted within 48 hours. 10x silver carboxylate demonstrated superior antimicrobial activity to antibiotics and other silver formulations and showed minimal cytotoxicity compared with other silver formulations. Current antimicrobial therapies in wound care and surgical antisepsis, such as chlorhexidine gluconate, have pitfalls including poor skin penetration and short duration of efficacy. The broad antimicrobial activity, extended elution, and deep skin penetration of this AgCar formulation show great promise for surgical site infection and wound care treatment. Novel technology to fight the growing threat of microbial resistance should be at the forefront of orthopaedic surgical site infection prevention and treatment.

Spatially resolved fluoroalkylation and alkylation of graphene by direct laser writing.

Two classes of photoactive compounds containing fluoroalkyl- and alkyl silver carboxylates were utilized for graphene laser writing, affording a set of patterned graphene architectures bearing various functionalities. The laser patterning of graphene is accomplished by using laser-triggered decomposition of silver carboxylates to generate radicals confined to the irradiated area for the selective binding of graphene.

Tailoring Morphology and Size of Silver Nanoparticles Prepared by Polyol Method by Changing the Structure of Silver Carboxylate Precursor

AbstractSilver nanoparticles are synthesized by reducing silver alkyl carboxylates at their high concentrations with ethylene and propylene glycol without a common use of polymeric dispersants and stabilizers. The effects of alkyl chain structure on the morphology and size of silver particles have been studied by scanning electron microscopy, transmission electron microscopy, powder X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analyses. The carboxylates that have been investigated are silver caprylate, laurate, 2‐butyloctanoate, and 2‐ethylhexanoate. It was found that the reduction temperature of straight‐chain alkyl carboxylates is in the 110–120 °C range. The particles prepared under these conditions are perfectly spherical in shape and their average size varies from 20 to 40 nm. In the case of the branched structure, the reduction process starts at around 80 °C and produces irregularly shaped silver particles with a size of 150 to 450 nm. Possible ways of controlling the parameters of the synthesized nanoparticles are proposed. This study proposes a simple and easily scalable method to prepare silver nanoparticles stabilized by a non‐polymeric stabilizer. The as‐synthesized silver particles may have applications as metallic fillers in ink and paste formulations for 2D and 3D printing to fabricate functional components and devices.

Functionalization of fullerene soot through oxidative decarboxylative coupling with silver dinitrobenzoate

In this research, we extend the functionalization of fullerene soot with nitroaryl substituents through oxidative decarboxylative coupling with silver 3,5-dinitrobenzoate. For this purpose, silver 3,5-dinitrobenzoate is first prepared in two-steps from 3,5-dinitrobenzoic acid. Then, this compound as a substrate together with potassium persulfate as an oxidant is used in acetonitrile as a solvent to functionalize fullerene soot. The reactions with different equivalent ratios of substrate and oxidant are conducted by both thermal and microwave conditions. This strategy is able to induce about 88.03 wt.% O and 5.79 wt.% N to the composition of fullerene soot. The advantage of this strategy is that the reaction can happen without the need for a catalyst, because silver(I) present in the substrate can catalyze the reaction progress. To prove the functionalization, several characterization techniques are used, i.e. XRD patterns, EDX spectra and SEM elemental distribution images, FE-SEM and TEM micrographs, particle size distribution histograms, FT-IR and Raman spectra, as well as TGA and DSC curves, which demonstrate the changes on fullerene soot. The novelty of this research is that it provides a new strategy for oxidative decarboxylative coupling of silver(I) carboxylates with the carbon surface.

Gold-Catalyzed C-O Cross-Coupling Reactions of Aryl Iodides with Silver Carboxylates.

We have developed a C-O cross-coupling reaction of (hetero)aryl iodides with silver carboxylates via a AuI/AuIII catalytic cycle. The transformation featured exclusive chemoselectivity and moisture/air insensitivity. Aromatic and aliphatic (including primary, secondary, and tertiary) silver carboxylates are all suitable substrates. Moreover, this protocol worked well intermolecularly and intramolecularly. Most importantly, good yields were obtained regardless of the substrates' electronic effect and steric hindrance.

Ligand Size and Carbon-Chain Length Study of Silver Carboxylates in Focused Electron-Beam-Induced Deposition.

Gas-assisted focused electron-beam-induced deposition is a versatile tool for the direct writing of complex-shaped nanostructures with unprecedented shape fidelity and resolution. While the technique is well-established for various materials, the direct electron beam writing of silver is still in its infancy. Here, we examine and compare five different silver carboxylates, three perfluorinated: [Ag2(µ-O2CCF3)2], [Ag2(µ-O2CC2F5)2], and [Ag2(µ-O2CC3F7)2], and two containing branched substituents: [Ag2(µ-O2CCMe2Et)2] and [Ag2(µ-O2CtBu)2], as potential precursors for focused electron-beam-induced deposition. All of the compounds show high sensitivity to electron dissociation and efficient dissociation of Ag-O bonds. The as-deposited materials have silver contents from 42 at.% to above 70 at.% and are composed of silver nano-crystals with impurities of carbon and fluorine between them. Precursors with the shortest carbon-fluorine chain ligands yield the highest silver contents. In addition, the deposited silver content depends on the balance of electron-induced ligand co-deposition and ligand desorption. For all of the tested compounds, low electron flux was related to high silver content. Our findings demonstrate that silver carboxylates constitute a promising group of precursors for gas-assisted focused electron beam writing of high silver content materials.

Synthesis of Benzylic Alcohols by Decarboxylative Hydroxylation.

Herein, we demonstrate an efficient method for the decarboxylative hydroxylation of carboxylic acids with silver(I) as the catalyst and cerium ammonium nitrate as the oxidant and its utility in chemoselective late-stage functionalization of natural products and drug molecules. The chemoselectivity of this protocol arises from a benzylic nitrate intermediate that retards further oxidation and is hydrolyzed to the final benzylic alcohol product. Mechanistic investigation reveals that the facile oxidation of silver carboxylate affords silver(II) species as an intermediate oxidant responsible for decarboxylation.

Silver Carboxylate-Eluting Titanium-Dioxide Polydimethylsiloxane Coating Inhibits Multi-Drug-Resistant Acinetobacterium baumannii and Vancomycin-Resistant Enterococcus faecalis Adherence and Proliferation on Orthopedic Trauma Fixation and Spinal Fusion Materials.

Background: Vancomycin-resistant Enterococcus faecalis and multi-drug-resistant (MDR) Acinetobacter baumannii are rising contributors to spinal fusion and fracture-associated infections (FAI), respectively. These MDR bacteria can form protective biofilms, complicating traditional antibiotic treatment. This study explores the effects of the antibiotic-independent antimicrobial silver carboxylate (AgCar)-doped coating on the adherence sand proliferation of these pathogens on orthopedic implant materials utilized in spinal fusion and orthopedic trauma fixation. Methods: Multi-drug-resistant Acinetobacter baumannii and vancomycin-resistant Enterococcus faecalis were inoculated on five common implant materials: cobalt chromium, titanium, titanium alloy, polyether ether ketone, and stainless steel. Dose response curves were generated to assess antimicrobial potency. Scanning electron microscopy and confocal laser scanning microscopy were utilized to characterize and quantify growth and adherence on each material. Results: The optimal AgCar concentration was a 95% titanium dioxide (TiO2)-5% polydimethylsiloxane (PDMS) matrix combined with 10 × silver carboxylate, which inhibited bacterial proliferation by 89.40% (p = 0.001) for MDR Acinetobacter baumannii and 84.02% (p = 0.001) for vancomycin-resistant Enterococcus faecalis compared with uncoated implants. A 95% TiO2-5% PDMS matrix combined with 10 × AgCar was equally effective at inhibiting bacterial proliferation across all implant materials for MDR Acinetobacter baumannii (p = 0.19) and vancomycin-resistant Enterococcus faecalis (p = 0.07). A 95% TiO2-5% PDMS matrix with 10 × AgCar is effective at decreasing bacterial adherence of both MDR Acinetobacter baumannii and vancomycin-resistant Enterococcus faecalis on implant materials. Conclusions: Application of this antibiotic-independent coating for surgery in which these implant materials might be used may prevent adherence, biofilm formation, spinal infections, and FAI by MDR Acinetobacter baumannii and vancomycin-resistant Enterococcus faecalis.

Silver as an Antibiotic-Independent Antimicrobial: Review of Current Formulations and Clinical Relevance.

Background: The increase of multi-drug-resistant organisms has revived the use of silver as an alternative antibiotic-independent antimicrobial. Although silver's multimodal mechanism of action provides low risk for bacterial resistance, high local and uncontrolled concentrations have shown toxicity. This has resulted in efforts to develop novel silver formulations that are safer and more predictable in their application. Optimization of silver as an antimicrobial is crucial given the growing resistance profile against antibiotics. This article reviews formulations of silver used as antimicrobials, focusing on the mechanisms of action, potential for toxicity, and clinical applications. Methods: A search of four electronic databases (PubMed, Embase, MEDLINE, and Cochrane Library) was conducted for relevant studies up to January 2022. Searches were conducted for the following types of silver: ionic, nanoparticles, colloidal, silver nitrate, silver sulfadiazine, silver oxide, silver carboxylate, and AQUACEL® (ConvaTec, Berkshire, UK). Sources were compiled based on title and abstract and screened for inclusion based on relevance and study design. Results: A review of the antimicrobial activity and uses of ionic silver, silver nanoparticles, colloidal silver, silver nitrate, silver sulfadiazine, silver oxide, Aquacel, and silver carboxylate was conducted. The mechanisms of action, clinical uses, and potential for toxicity were studied, and general trends between earlier and more advanced formulations noted. Conclusions: Early forms of silver have more limited utility because of their uncontrolled release of silver ions and potential for systemic toxicity. Multiple new formulations show promise; however, there is a need for more prospective in vivo studies to validate the clinical potential of these formulations.

Silver ionic compounds as a source of metal carriers in the gas phase

In the present study, we have synthesised and characterised new silver(I) complexes with the general formula [Ag(NH2tBu)2](RfCO2)·xH2O, where Rf = CF3, x = 0.5; Rf = C2F5, C5F11, C6F13, x = 0; and [Ag(NH2tBu)2][Ag(NH2tBu)2(H2O)](RfCO2)2·xH2O, where Rf = C3F7, x = 0.25; Rf = C4F9, x = 0. Single crystal X-ray diffraction, infrared spectroscopy (IR) and nuclear magnetic resonance (NMR) spectroscopy were used to confirm compounds’ composition and structure. The volatility of the compounds was studied using thermal analysis, electron impact (EI) mass spectrometry, variable temperature infrared spectroscopy, and sublimation experiments. Research has revealed that when compounds are heated, their structures are changed, and volatile silver carboxylates are formed. A thermal decomposition mechanism over reduced pressure was proposed. Two compounds [Ag(NH2tBu)2](CF3CO2)·0.5H2O and [Ag(NH2tBu)2](C2F5CO2) were used in chemical vapour deposition experiments with an evaporation temperature of 473 K and a decomposition temperature in the range of 593–653 K without the using of additional reducing agents such as hydrogen. Due to the low efficiency of generating volatile metal carriers, very thin deposits containing silver were obtained.

In Situ Time-of-Flight Mass Spectrometry of Ionic Fragments Induced by Focused Electron Beam Irradiation: Investigation of Electron Driven Surface Chemistry inside an SEM under High Vacuum.

Recent developments in nanoprinting using focused electron beams have created a need to develop analysis methods for the products of electron-induced fragmentation of different metalorganic compounds. The original approach used here is termed focused-electron-beam-induced mass spectrometry (FEBiMS). FEBiMS enables the investigation of the fragmentation of electron-sensitive materials during irradiation within the typical primary electron beam energy range of a scanning electron microscope (0.5 to 30 keV) and high vacuum range. The method combines a typical scanning electron microscope with an ion-extractor-coupled mass spectrometer setup collecting the charged fragments generated by the focused electron beam when impinging on the substrate material. The FEBiMS of fragments obtained during 10 keV electron irradiation of grains of silver and copper carboxylates and shows that the carboxylate ligand dissociates into many smaller volatile fragments. Furthermore, in situ FEBiMS was performed on carbonyls of ruthenium (solid) and during electron-beam-induced deposition, using tungsten carbonyl (inserted via a gas injection system). Loss of carbonyl ligands was identified as the main channel of dissociation for electron irradiation of these carbonyl compounds. The presented results clearly indicate that FEBiMS analysis can be expanded to organic, inorganic, and metal organic materials used in resist lithography, ice (cryo-)lithography, and focused-electron-beam-induced deposition and becomes, thus, a valuable versatile analysis tool to study both fundamental and process parameters in these nanotechnology fields.

Synergistic Effects of Silver Carboxylate and Chlorhexidine Gluconate for Wound Care and Prevention of Surgical Site Infections by Cutibacterium acnes and Methicillin-Resistant Staphylococcus aureus.

Background: This study presents the effectiveness of a combined silver carboxylate (AgCar) and chlorohexidine gluconate (AgCar:CHG) chemistry assessed against two commonly encountered nosocomial pathogens, Methicillin-resistant Staphylococcus aureus (MRSA) and Cutibacterium acnes, within the context of surgical antisepsis and wound care. Methods: Through an Institutional Review Board- and Institutional Animal Care and Use Committee (IACUC)-approved protocol, AgCar:CHG was applied to live Yucatan porcine skin and visualized by fast red and green staining to assess level of skin penetration. Dose response curves for Cutibacterium acnes and MRSA were generated to determine the optimal therapeutic ratio of AgCar to CHG. Coatings were applied to two different clinically available sutures and antimicrobial efficacy was evaluated at 24-hour intervals using Kirby-Bauer (KB) assays. Graphite furnace atomic absorption spectroscopy was used to measure AgCar elution from sutures over time. Results: Synergistic application of AgCar:CHG demonstrated deep pilosebaceous gland penetration on Yucatan pig skin. The therapeutic concentration range of AgCar was determined to be between 120 × -150 × and 30 × -60 × dopage for MRSA and Cutibacterium acnes, respectively. A 1:1 therapeutic ratio of AgCar to CHG was found to have 100% bactericidal activity against both pathogens. Sutures coated with AgCar:CHG showed sustained antimicrobial activity against MRSA and Cutibacterium acnes, and were significantly more efficacious than antimicrobial sutures over the three- to four-day period (p < 0.01). Conclusions: This AgCar:CHG chemistry demonstrates deep skin penetration, extended elution, and broad-spectrum antimicrobial activity compared with commercially available options. This chemistry shows promise as an additional tool for the prophylaxis of surgical site infections.

Silver Carboxylate as an Antibiotic-Independent Antimicrobial: A Review of Current Formulations, in vitro Efficacy, and Clinical Relevance.

The increasing prevalence of multi-drug resistant pathogens has led to a renewed focus on the use of silver as an antibiotic-independent antimicrobial. Unfortunately, the use of many silver formulations may be limited by an uncontrolled release of silver with the potential for significant cytotoxic effects. Silver carboxylate (AgCar) has emerged as an alternative formulation of silver with the potential to mitigate these concerns while still displaying significant bactericidal activity. This article reviews the efficacy of silver carboxylate formulations as a promising novel antibiotic-independent antimicrobial. This study was conducted through a search of five electronic databases (PubMed, Embase, MEDLINE, Cochrane Library, and Web of Science) for relevant studies up to September 2022. Searches were conducted for types of "silver carboxylate" formulations. Sources were compiled based on title and abstract and screened for inclusion based on relevance and study design. A review of the antimicrobial activity and cytotoxicity of silver carboxylate was compiled based on this search. Current body of data suggests that silver carboxylate shows promise as an emerging antibiotic-independent antimicrobial, with significant bactericidal effects while minimizing cytotoxicity. Silver carboxylate addresses several of the limitations of more primitive formulations, including controlled dosing and fewer negative effects on eukaryotic cell lines. These factors are concentration-dependent and largely rely on the vehicle system used to deliver it. Although several silver carboxylate-based formulations like titanium dioxide/polydimethylsiloxane (TiO2/PDMS) matrix-eluting AgCar have shown promising results in vitro, and could potentially be utilized independently or in conjunction with current and future antimicrobial therapies, there is a need for further in vivo studies to validate their overall safety and efficacy profile.

Zinc and Silver Salts-Containing Lamellar Titanium Phosphate: A Multifunctional Filler

Zinc and silver compounds have been studied because they have ultraviolet light barrier properties and bactericidal action, respectively. Materials with multifunctional characteristics have been sought to produce polymeric nanocomposites. In this work, the chemical modification of titanium phosphate (TiP) was carried out through a route with successive intercalations. TiP was synthesized and consecutively pre-expanded with ethylamine and pyromellitic acid. Then it was modified with zinc acetate and silver nitrate. The final product was characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, wide-angle X-ray diffractometry, field emission scanning electron microscopy coupled with energy dispersive X-ray spectroscopy and thermogravimetry. Infrared revealed dislocation and appearance of bands according to the intercalating agent. Inorganic salts interfered in the crystallization and melting processes of pyromellitic acid. Vanishing of the TiP hkl plane and variation and appearance of new crystallographic planes at low diffraction angles induced intercalation. SEM showed agglomerated structures. New thermal degradation events at higher temperatures endorsed the formation of zinc and silver carboxylate salts. We concluded that a new miscellaneous and multifunctional matter was achieved.

The cobalt(ii)-catalyzed acyloxylation of picolinamides with bifunctional silver carboxylateviaC–H bond activation

The cobalt(ii)-catalyzed C–H bond acyloxylation of picolinamides with bifunctional silver carboxylate has been developed. The mild and practical esterification provides an atom-economic route to access to polysubstituted naphthalene compounds.

Silver carboxylate-doped titanium dioxide-polydimethylsiloxane coating decreases Cutibacterium acnes adherence and biofilm formation on polyether ether ketone

BACKGROUND CONTEXTCutibacterium acnes (C. acnes) is a gram-positive facultative anaerobe found in the deep sebaceous follicles of the skin on the shoulder and back. C. acnes has been increasingly recognized as a pathogen in spinal surgical site infection (SSI) especially in the presence of instrumentation. PURPOSEThis study assesses whether a silver carboxylate-doped titanium dioxide-polydimethylsiloxane (TiO2-PDMS) coating can decrease C. acnes adherence and biofilm formation on PEEK and four other commonly used spinal implant materials, stainless steel, cobalt chromium, titanium, and titanium alloy. STUDY DESIGNWe compared the adherence of C. acnes over 24 hours between uncoated, 95:5 TiO2 to PDMS ratio with 10× silver carboxylate coating and a 100% silver carboxylate coating on each implant material, which were uniformly saw cut and sterilized. Implants were then subjected to scanning electron microscopy (SEM) and confocal scanning laser microscopy (CSLM). METHODSSamples were coated using 95:5 TiO2-PDMS 10× silver carboxylate, 100% silver carboxylate, or left uncoated. C. acnes was applied onto the samples and allowed to adhere for periods of 4, 8, 12, 16, or 20 hours. Nonadherent bacteria were then washed from the samples. These samples were then allowed to continue incubating for a total of 24 hours. SEM and confocal laser scanning microscope were used to visualize all samples for the presence of biofilm and quantification of C. acnes adherence at each time point. RESULTSThe 95:5 TiO2-PDMS 10× silver carboxylate coating was able to significantly decrease C. acnes adherence on PEEK after 8, 12, 16, and 20 hours of adherence. No statistical difference was found between the 95:5 TiO2-PDMS 10× silver carboxylate coating and the 100% silver carboxylate positive control. We previously observed extensive C. acnes biofilm formation on uncoated PEEK, but none on PEEK coated with either the 95:5 TiO2-PDMS 10× silver carboxylate or 100% Ag coating . Furthermore, no biofilm formation was observed on stainless steel, cobalt chromium, titanium, and titanium alloy coated with 95:5 TiO2-PDMS 10× silver carboxylate or 100% Ag coating. CONCLUSIONA 95:5 TiO2-PDMS 10× silver carboxylate coating decreases C. acnes adhesion and prevents biofilm formation on PEEK and other common orthopedic implant materials. CLINICAL SIGNIFICANCEA 95:5 TiO2-PDMS 10× silver carboxylate coating may help decrease spinal SSI due to C. acnes, especially in procedures with instrumentation.

Silver carboxylate and titanium dioxide-polydimethylsiloxane coating decreases adherence of multi-drug resistant Serratia marcescens on spinal implant materials.

The opportunistic multi-drug resistant nosocomial gram negative bacilli Serratia marcescens (S. marcescens) is a rising contributor to spinal implant infections (Iguchi et al., Genome Biol Evol 6:2096-2110, 2014; Teresa et al., J Clin Microbiol 55:2334-2347; Dante et al., J Clin Microbiol 54:120-126). This study investigates the most effective matrix ratio of an antibiotic-independent, silver carboxylate-doped titanium dioxide (TiO2)-polydimethylsiloxane (PDMS) coating in preventing adherence of multidrug resistant pathogen S. marcescens to spinal implant materials. This project examined an antibiotic-independent, silver carboxylate-doped titanium dioxide (TiO2)-polydimethylsiloxane (PDMS) coating on three common spinal implant materials, polyetheretherketone (PEEK), stainless steel (SS), and titanium (Ti), which previously were found to be prone to bacterial adhesion (Garcia et al., Spine Deform 8:351-359). After generation of dose response curves to find the optimal silver carboxylate concentration, 95% TiO2-5% PDMS was combined with 10× silver carboxylate and compared to 100% silver carboxylate and uncoated implants. Implants were imaged using scanning electron microscopy and confocal laser scanning microscopy to detect adherent S. marcescens. Ninety-five percent TiO2-5% PDMS and 10× silver carboxylate coating decreased adherence of S. marcescens on PEEK by 99.61% (p = 0.001), on titanium by 98.77% (p = 0.001), and on stainless steel by 88.10% (p = 0.001) after 24h. The average decrease in bacterial adherence was 95.49% compared to uncoated implants. A coating composition comprised of 95% TiO2-5% PDMS matrix and 10× silver carboxylate most effectively decreases adherence of S. marcescens on spinal implants. These results suggest that the application of a non-antibiotic, bactericidal coating prior to spinal surgery may prevent the adherence and proliferation of MDR S. marcescens and decrease the incidence of spinal SSI.

Expanded Ring NHC Silver Carboxylate Complexes as Efficient and Reusable Catalysts for the Carboxylative Cyclization of Unsubstituted Propargylic Derivatives.

Stabilized by a bulky N‐heterocyclic carbene [BPDPr, 1,3‐bis(2,6‐diisopropylphenyl)‐1,3‐diazonine‐2‐ylidene] ligand, new silver carboxylate complexes of the form BPDPrAgO2C‐R (R=Me, Ph) have been synthesized and fully characterized in solution and in the solid state and implemented as sole catalysts (base‐, additive‐, and, in some cases, solvent‐free) in the challenging fixation of carbon dioxide to unsubstituted propargylic derivatives for the synthesis of oxazolidinones and α‐methylene cyclic carbonates. Derived from X‐ray diffraction studies, the molecular geometry and the concept of buried volume were employed to describe the structural and steric features of these silver complexes. Their stability and efficiency as catalysts have been demonstrated by the synthesis of 29 carboxylation products (72–98 % yield) at low catalyst loadings (0.01–1.5 mol%). Characteristics are high turnover numbers (up to 9400), catalyst recyclability (up to 96 % yield after the 7th cycle with no decomposition of the silver complex), and the possibility to scale‐up the reaction.

Vacuum versus ambient pressure inert gas thermogravimetry: a study of silver carboxylates

A comparative study of vacuum versus ambient pressure inert gas thermogravimetry was performed on silver carboxylates compounds. Some of the complexes from this group have been previously successfully applied as precursors for both chemical vapour deposition and electron beam-induced deposition. Considerable differences were found between the thermogravimetry methods, which we associate with changes in evaporation dynamics. Vacuum thermogravimetry sublimation onsets consistently occurred at lower temperatures than ambient pressure N2-flow thermogravimetry, where the differences reached up to 120 °C. Furthermore, compound sublimation during N2-TGA was suppressed to such an extent that significant thermal decomposition of the compounds into metal and volatile organic fragments was observed while at vacuum the same complexes sublimed as intact molecules. Moreover, thermal stability of silver complexes was investigated using isothermal thermogravimetry. These findings are interesting for the field of thin film synthesis and nanomanufacturing via chemical vapour deposition, atomic layer deposition and focused electron beam induced deposition. In all three methods, delivery of functional precursor over the substrate is crucial. The presented results prove that vacuum thermogravimetry can be used as fast method of pre-screening for novel, especially low-volatility precursors.Graphic abstract