First homoleptic MIC and heteroleptic NHC-MIC coordination cages from 1,3,5-triphenylbenzene-bridged tris-MIC and tris-NHC ligands

The preparation of a triphenylbenzene-bridged tris-(1,2,3-triazolium) salt allowed us to obtain the first homoleptic tris-MIC cylinder-like cages of Ag and Au. The silver MIC-based cage reacts with the trisNHC-Ag analogue to form the corresponding heteroleptic NHC–MIC silver cage in an unusual reaction involving the simultaneous exchange of the tris-NHC and tris-MIC ligands.MINECO (CTQ2014-51999-P) and UJI (P11B2014-02).Published versio

Visible-light-promoted iridium(III)-catalyzed acceptorless dehydrogenation of N-Heterocycles at room temperature

An effective visible-light-promoted iridium(III)catalyzed hydrogen production from N-heterocycles is described. A single iridium complex constitutes the photocatalytic system playing a dual task, harvesting visible-light and facilitating C-H cleavage and H-2 formation at room temperature and without additives. The presence of a chelating C-N ligand combining a mesoionic carbene ligand along with an amido functionality in the Ir-III complex is essential to attain the photocatalytic transformation. Furthermore, the le l complex is also an efficient catalyst for the thermal reverse process under mild conditions, positioning itself as a proficient candidate for liquid organic hydrogen carrier technologies (LOHCs). Mechanistic studies support a light-induced formation of H-2 from the Ir-H intermediate as the operating mode of the iridium complex

Post-Modification of the Electronic Properties by Addition of π-Stacking Additives in N-Heterocyclic Carbene Complexes with Extended Polyaromatic Systems

A series of iridium complexes containing phenanthro[4,5-abc]phenazino[11,12-d]imidazol-2-ylidene and acetonaphtho[1,2-b]quinoxaline[11,12-d]imidazol-2-ylidene ligands have been obtained and fully characterized. These complexes display highly extended polyaromatic systems attached to the backbone of the N-heterocyclic carbene. The presence of this extended polyaromatic system makes the electron-donating character of these ligands sensitive to the presence of π-stacking additives, such as pyrene and hexafluorobenzene. The computational studies predict that the addition of pyrene affords an increase of the electron-donating character of the polyaromatic ligand (TEP decreases), while the addition of hexafluorobenzene has the opposite effect (TEP increases). This prediction is experimentally corroborated by IR spectroscopy, by measuring the shift of the CO stretching bands of a series of IrCl(NHC)(CO)2 complexes, where NHC is the N-heterocyclic carbene ligand with the polyaromatic system. Finally, the energy of the π-stacking interaction of one of the key Ir(I) complexes with pyrene and hexafluorobenzene has been estimated by using the Benesi-Hildebrand treat-ment, based on the δ-shifts observed by 1H NMR spectroscopy.MEC of Spain (CTQ2011-24055/BQU

SARS-CoV-2 viral load in nasopharyngeal swabs is not an independent predictor of unfavorable outcome

The aim was to assess the ability of nasopharyngeal SARS-CoV-2 viral load at first patient’s hospital evaluation to predict unfavorable outcomes. We conducted a prospective cohort study including 321 adult patients with confirmed COVID-19 through RT-PCR in nasopharyngeal swabs. Quantitative Synthetic SARS-CoV-2 RNA cycle threshold values were used to calculate the viral load in log10 copies/mL. Disease severity at the end of follow up was categorized into mild, moderate, and severe. Primary endpoint was a composite of intensive care unit (ICU) admission and/or death (n = 85, 26.4%). Univariable and multivariable logistic regression analyses were performed. Nasopharyngeal SARS-CoV-2 viral load over the second quartile (≥ 7.35 log10 copies/mL, p = 0.003) and second tertile (≥ 8.27 log10 copies/mL, p = 0.01) were associated to unfavorable outcome in the unadjusted logistic regression analysis. However, in the final multivariable analysis, viral load was not independently associated with an unfavorable outcome. Five predictors were independently associated with increased odds of ICU admission and/or death: age ≥ 70 years, SpO2, neutrophils > 7.5 × 103/µL, lactate dehydrogenase ≥ 300 U/L, and C-reactive protein ≥ 100 mg/L. In summary, nasopharyngeal SARS-CoV-2 viral load on admission is generally high in patients with COVID-19, regardless of illness severity, but it cannot be used as an independent predictor of unfavorable clinical outcome

Catalytic conversion of alkynes to α-vinyl sulfides mediated by carbene-linker-carbene (CXC) rhodium and iridium complexes

Abstract The catalytic activity of a set of mono- and bimetallic Rh(I) and Ir(I) complexes bearing carbene-linker-carbene (CXC) bis-triazolylidene ligands (with X = O, N) coordinated in a bridging or chelating fashion was evaluated in the hydrothiolation of alkynes. The hydrothiolation of 1-hexyne with thiophenol in the absence of an external base or other additives was selected as a model reaction. All rhodium complexes are highly selective catalysts towards Markovnikov product formation and display superior activity compared to the related iridium derivatives. DFT calculations were carried out to rationalize the reaction mechanism and selectivity of this process. Neutral dinuclear [Rh₂Cl₂(cod)₂(μ-COC)] was found to be the most effective catalyst for this transformation. Its applicability was further studied towards the hydrothiolation of different alkyl and aryl alkynes using predominantly aryl thiols and proved to be one of the most active and selective catalysts towards the α-vinyl sulfide product to date

Power factor improvement in a solid–liquid thermoelectric system formed by Sb:SnO₂ in contact with a chromium complex solution

Thermoelectric (TE) materials can convert heat into electricity. Good TE materials should have high power factors (PF) and low thermal conductivities. PF = S2σ is governed by the Seebeck coefficient S and the electrical conductivity σ. Most recent improvements in TE materials performance have been achieved by the reduction of the thermal conductivity, and strategies to improve the PF have been minor. Recently, an innovative concept to significantly increase the PF, based on the combination of a porous TE solid with an electrolyte, has been reported. Here, we make use of this new approach but using an electroactive salt (redox molecule) solution as electrolyte, rather than the non-electroactive electrolytes and ionic liquids previously employed. A system formed by a nanostructured and porous Sb:SnO2 film in contact with Cr(III) acetylacetonate dissolved in 3-methoxypropionitrile was prepared. Using this electrolyte, an average PF enhancement of 3.4 times was achieved, due to an average decrease of 23.2% and 82.8% in the absolute value of the Seebeck coefficient and the electrical resistivity of the solid, respectively. An impedance spectroscopy analysis, after checking by scanning electron microscopy and energy-dispersive X-ray spectroscopy that no changes take place in the Sb:SnO2 film due to the presence of electrolytes, revealed that the improvements come from the donation of electrons from the electrolyte to the solid, which increases its electrical conductivity and the usual drop in the Seebeck coefficient. The remarkable PF improvement obtained is among the highest reported and opens a new way of significantly enhancing this parameter

Strongly Coordinating Ligands To Form Weakly Coordinating Yet Functional Organometallic Anions

Weakly coordinating anions (WCAs) are generally tailored to act as spectators with little or no function. Here we describe the implementation of strongly coordinating dianionic carboranyl N-heterocyclic carbenes (NHCs) to create organometallic -ate complexes of Au(I) that serve both as WCAs and functional catalysts. These organometallic WCAs can be utilized to form both heterobimetallic (Au(I)−/Ag(I)+; Au(I)−/Ir(I)+) and organometallic/main group ion pairs (Au(I)−/(CPh3+ or SiEt3+). Because parent unfunctionalized dianionic carboranyl NHC complex 3 is unstable in most solvents when paired with CPh3+, novel synthesis methodology was devised to create polyhalogenated carboranyl NHCs, which show superior stability toward electrophilic substitution and cyclometalation chemistry. Additionally, the WCAs containing polyhalogenated carboranyl NHCs are among the most active catalysts reported for the hydroamination of alkynes. This investigation has also produced the first examples of a low-coordinate Au(III) center with two cis accessible coordination sites and the first true dianionic carbene. These studies pave the way for the design of functional ion pairs that have the potential to participate in tandem or cooperative small-molecule activation and catalysis

1,2,3-triazolin-5-ylidenes: Synthesis of hetero-bis(carbene) Pd(II) complexes, determination of donor strengths, and catalysis

10.1021/om2010029Organometallics311405-412ORGN