Synthesis and Photophysical Properties of T-Shaped Coinage-Metal Complexes.

The photophysical properties of a series of T-shaped coinage d10 metal complexes, supported by a bis(mesoionic carbene)carbazolide (CNC) pincer ligand, are explored. The series includes a rare new example of a tridentate T-shaped AgI complex. Post-complexation modification of the AuI complex provides access to a linear cationic AuI complex following ligand alkylation, or the first example of a cationic square planar AuIII -F complex from electrophilic attack on the metal centre. Emissions ranging from blue (CuI ) to orange (AgI ) are obtained, with variable contributions of thermally-dependent fluorescence and phosphorescence to the observed photoluminescence. Green emissions are observed for all three gold complexes (neutral T-shaped AuI , cationic linear AuI and square planar cationic AuIII ). The higher quantum yield and longer decay lifetime of the linear gold(I) complex are indicative of increased phosphorescence contribution.

A Hemilabile and Cooperative N-Donor-Functionalized 1,2,3-Triazol-5-Ylidene Ligand for Alkyne Hydrothiolation Reactions.

A series of novel cationic and neutral Rh complexes with an N-donor-functionalized 1,2,3-triazol-5-ylidene (TRZ) ligand (in which the pendant N donor is NHBoc, NH2 , or NMe2 ) is described. The catalytic activity of these complexes was evaluated in the hydrothiolation of alkynes. Among the catalysts, a neutral dicarbonyl complex featuring the tethered-NBoc amido-TRZ ligand proved very selective for alkyne hydrothiolation with an aryl thiol. Remarkably, the reaction could be carried out in the absence of pyridine or base additive. In addition, during the reaction, no evidence for oxidative addition of the thiol S-H bond was observed, strongly suggesting a reaction pathway in which a bifunctional ligand is involved. Experimental and theoretical mechanistic investigations suggest a ligand-assisted deprotonation of thiol, hemilabile dissociation of amine from the metal, and thiolate coordination, which is indicative of a different reaction mechanism to those previously reported for related alkyne hydrothiolation reactions.

Nucleophilic T-Shaped (LXL)Au(I)-Pincer Complexes: Protonation and Alkylation.

We report the synthesis and reactivity of unusual T-shaped (LXL)Au(I)-pincer complexes, based on a carbazole framework flanked by two mesoionic carbenes (MICs). In contrast to other Au(I) complexes, these complexes react with electrophiles. Protonation and alkylation occur either at the metal or the ligand, depending on steric factors. Of particular interest, protonation at gold leads to an unprecedented cationic Au(III) hydride, which gives a 1H NMR resonance at δ -8.34 ppm. The reactivity of this "hydride", however, shows protic and not hydridic behavior.

Substituent effects on the electrochemical, spectroscopic, and structural properties of Fischer mono- and biscarbene complexes of chromium(0).

A series of ten ferrocenyl, furyl, and thienyl mono- and biscarbene chromium(0) complexes were synthesized and characterized spectroscopically and electrochemically. The single crystal structure of the biscarbene complex [(CO)5Cr═C(OEt)-Fu'-(OEt)C═Cr(CO)5] (4a) was determined: C20H12Cr2O13; triclinic; P1; a = 6.2838(5), b = 12.6526(9), c = 29.1888(19) Å, α = 89.575(2), ß = 88.030(2), γ = 87.423(2)°; Z = 4. Results from an electrochemical study in CH2Cl2 were mutually consistent with a computational study in showing that the carbene double bond of 1-6 is reduced to an anion radical, (-)Cr-C• at formal reduction potentials < -1.7 V vs FcH/FcH(+). The Cr centers are oxidized in two successive one electron transfer steps to Cr(II) via the Cr(I) intermediate. Only Cr(I) oxidation is electrochemically irreversible. Dicationic Cr(II) species formed upon two consecutive one-electron oxidation processes are characterized by a peculiar bonding situation as they are stabilized by genuine CH···Cr agostic interactions. With respect to aryl substituents, carbene redox processes occurred at the lowest potentials for ferrocene derivatives followed by furan complexes. Redox process in the thiophene derivatives occurred at the highest potentials. This result is mutually consistent with a (13)C NMR study that showed the Cr═C functionality of furyl complexes were more shielded than thienyl complexes. The NHBu carbene substituent resulted in carbene complexes showing redox processes at substantially lower redox potentials than carbenes having OEt substituents.

2-(Biphenyl-4-yl)propan-2-ol.

The title compound, C(15)H(16)O, crystallizes with two independent mol-ecules in the asymmetric unit. Due to the space-group symmetry, this results in the formation of a tetra-mer where the four mol-ecules are connected by O-H⋯O hydrogen bonds. The mol-ecules pack parallel to the c axis. Both mol-ecules in the asymmetric unit are nonplanar and the dihedral angles between connected aromatic rings in each mol-ecule are 7.96 (12) and 9.75 (13)°. This contrasts with the gas phase density functional theory (DFT) optimized conformation, where this dihedral angle is 39.33°.

3,6-Diaza-octane-1,8-diaminium diiodide.

The asymmetric unit of the title salt, C(6)H(20)N(4) (2+)·2I(-), comprises half a 3,6-diaza-octane-1,8-diaminium dication plus an I(-) anion. The dications are symmetrical and lie across crystallographic centres of inversion. In the crystal, the ions form a network involving mainly weak N-H⋯I inter-molecular inter-actions: two H atoms of the ammonium group form inter-actions with two I(-) anions and the H atom of the secondary amine forms a weak inter-action with a third I(-) cation. The third ammonium H atom is hydrogen bonded to a secondary amine of an adjacent cation. The backbone of the cation does not form a uniformly trans chain, but is 'kinked' [C-N-C-C torsion angle = 71.5 (2)°], probably to accommodate the direct hydrogen bond between the ammonium group and the secondary amine in an adjacent cation.

2,2'-(Piperazine-1,4-di-yl)diethanaminium bis-(2-hy-droxy-benzoate).

The asymmetric unit of the title salt, C(8)H(22)N(4) (2+)·2C(7)H(5)O(3) (-), comprises half a 2,2'-(piperazine-1,4-di-yl)diethan-aminium dication plus a 2-hy-droxy-benzoate anion. In the crystal, the anions and cations are linked by N-H⋯O and O-H⋯O hydrogen bonds to form infinite two-dimensional networks parallel with the a unit-cell face. The conformation adopted by the cation in the crystal is very similar to that adopted by the same cation in the structures of the nitrate and tetra-hydrogen penta-borate salts.

2,2'-(Piperazine-1,4-di-yl)diethanaminium dibenzoate.

The asymmetric unit of the title salt C(8)H(22)N(4) (2+)·2C(7)H(5)O(2) (-), comprises two independent pairs of half a 2,2'-(piperazine-1,4-di-yl)diethanaminium dication plus a benzoate anion. The dications are symmetrical and lie across crystallographic centres of inversion. The crystal structure was refined as a two-component pseudo-merohedral twin using the twin law 001 0-10 100 [he domain fractions are 0.8645 (8) and 0.1355 (8)]. The anions and cations are linked by N-H⋯O hydrogen bonds and weak N-H⋯O inter-molecular inter-actions to form infinite two-dimensional networks parallel to [101]. The conformation adopted by the cation in the crystal structure is very similar to that adopted by the same cation in the structures of the 2-hy-droxy-benzoate [Cukrowski et al. (2012 ▶). Acta Cryst, E68, o2387], the nitrate and the tetra-hydrogen penta-borate salts.

{µ-5-[1,3-Bis(2,4,6-trimethyl-phen-yl)-3H-imidazolium-2-yl]-2-(2-oxoethenyl-1κC)furan-3-yl-2κC}-µ-hydrido-bis(tetra-carbonyl-rhenium) tetra-hydro-furan 0.67-solvate.

The title complex, [Re(2)(C(27)H(25)N(2)O(2))H(CO)(8)]·0.67C(4)H(8)O, was formed as a product in the reaction of a rhenium(I)-Fischer carbene complex with a free NHC carbene. The coordination environment about the two Re atoms is slightly distorted octahedral, including a bridging H atom. The imidazolium and furan groups are almost coplanar, whereas the mesityl substituents show an almost perpendicular arrangement with respect to both heterocyclic units. Mol-ecules of the complex pack in such a way as to form channels parallel with the bc unit-cell face diagonal running through the unit face diagonal. These channels are partially occupied by tetra-hydro-furan solvent mol-ecules.

[N,N'-Bis(2,4,6-trimethyl-phen-yl)ethane-1,2-diimine-κ(2)N,N']tetra-carbonyl-chromium(0).

The octa-hedral coordination of the Cr(0) atom in the title compound, [Cr(C(20)H(24)N(2))(CO)(4)], displays some distortion. This is manifested by an exocyclic torsion angle C(mesitylene)-N-Cr-C(carbon-yl) that deviates by more than 20° from planarity. Another structural feature is the significant distortion from linearity of the Cr-C-O angles of the two carbonyl groups that inter-act with both ortho-methyl groups of the two mesitylene rings. The remaining two carbonyl groups overlap with the centres of the mesitylene rings themselves and are linear within <3°.

Field-Scale Demonstration of PFAS Leachability Following In Situ Soil Stabilization.

A field-scale validation is summarized comparing the efficacy of commercially available stabilization amendments with the objective of mitigating per- and polyfluoroalkyl substance (PFAS) leaching from aqueous film-forming foam (AFFF)-impacted source zones. The scope of this work included bench-scale testing to evaluate multiple amendments and application concentrations to mitigate PFAS leachability and the execution of field-scale soil mixing in an AFFF-impacted fire-training area with nearly 2.5 years of post-soil mixing monitoring to validate reductions in PFAS leachability. At the bench scale, several amendments were evaluated and the selection of two amendments for field-scale evaluation was informed: FLUORO-SORB Adsorbent (FS) and RemBind (RB). Five ∼28 m3 test pits (approximately 3 m wide by 3 m long by 3 m deep) were mixed at a site using conventional construction equipment. One control test pit (Test Pit 1) included Portland cement (PC) only (5% dry weight basis). The other four test pits (Test Pits 2 through 5) compared 5 and 10% ratios (dry weight basis) of FS and RB (also with PC). Five separate monitoring events included two to three sample cores collected from each test pit for United States Environmental Protection Agency (USEPA) Method 1315 leaching assessment. After 1 year, a mass balance for each test pit was attempted comparing the total PFAS soil mass before, during, and after leach testing. Bench-scale and field-scale data were in good agreement and demonstrated >99% decrease in total PFAS leachability (mass basis; >98% mole basis) as confirmed by the total oxidizable precursor assay, strongly supporting the chemical stabilization of PFAS.

Characterization of per- and polyfluoroalkyl substances on fire suppression system piping and optimization of removal methods.

Fire suppression systems are known to be impacted with residual, entrained per- and polyfluoroalkyl substances (PFASs) because of historical use of aqueous film forming foam (AFFF) and fluoroprotein foam. Amphiphilic PFASs aggregate at liquid:solid interfaces creating a hydrophobic layer which reduces the effectiveness of water to remove PFAS from layered surfaces. When fire suppression systems are transitioned to fluorine free foam (F3) without appropriate cleaning, residual PFASs associated with the surfaces of the fire suppression system can contaminate the replacement F3. Release of residual PFASs from fire suppression systems into F3 has been documented; however, little is known about the residual PFASs associated with the surfaces of the fire suppression systems. More information is needed to develop methods to appropriately remove PFASs from fire suppression systems to prevent costly and inefficient foam transitioning and preserve the PFAS-free benefit of F3. The objective of this work was to evaluate the distribution and composition of PFASs on hangar piping exposed to PFAS-containing firefighting foam for a prolonged period. Two assessment methods were used: 1) extractions with methanol, water, and a proprietary aqueous organic solvent (Fluoro Fighter™); and 2) direct imaging methods of the surface. Extractions were analyzed with mass spectrometry and combustion ion chromatography. Results indicate pipe in contact with PFAS-containing firefighting foam can amass approximately 10 µg/cm2 of surface-associated PFAS residual following decades of exposure. Fluoro Fighter demonstrated higher PFAS removal per surface area of pipe than methanol (p = 0.007) or water extraction (p < 0.0001). Scanning electron microscope (SEM) images of the hangar piping reveal deposits suspected to be self-assembled PFAS layers, as evidenced by examination of pipe surfaces using X-ray photoelectron spectroscopy (XPS), which revealed atomic fluorine on the surface of the pipe.

Synthesis, characterization, and structural studies of multimetallic ferrocenyl carbene complexes of group VII transition metals.

Fischer carbene complexes of the group VII transition metals (Mn and Re) containing at least two or three different transition metal substituents, all in electronic contact with the carbene carbon atom, were synthesized. The structural features and their relevance to bonding in the carbene multimetal compounds were investigated, as they represent indicators of possible reactivity sites in polymetallic carbene assemblies. For complexes of the type [ML(x){C(OR)R'}] (ML(x) = MnCp(CO)(2) or Re(2)(CO)(9)), ferrocenyl (Fc) was chosen as the R' substituent, while the OR substituent was systematically varied between an ethoxy or a titanoxy group, to yield the complexes 1a (ML(x) = MnCp(CO)(2), R = Et, R' = Fc), 2a (ML(x) = MnCp(CO)(2), R = TiCp(2)Cl, R' = Fc), 3a (ML(x) = Re(2)(CO)(9), R = Et, R' = Fc), and 4a (ML(x) = Re(2)(CO)(9), R = TiCp(2)Cl, R' = Fc). Direct lithiation of the ferrocene with n-BuLi/TMEDA at elevated temperatures, followed by the Fischer method of carbene preparation, resulted in formation of the novel biscarbene complexes with bridging ferrocen-1,1'-diyl (Fc') substituents [{π-Fe(C(5)H(4))(2)-C,C'}{C(OEt)ML(x)}(2)] (1b, ML(x) = MnCp(CO)(2); 3b, ML(x) = Re(2)(CO)(9)) or the unusual bimetallacyclic bridged biscarbene complexes [{π-TiCp(2)O(2)-O,O'}{π-Fe(C(5)H(4))(2)-C,C'}{CML(x)}(2)] (2b, ML(x) = MnCp(CO)(2); 4b, ML(x) = Re(2)(CO)(9)). The target compounds that were isolated displayed a variety of different geometric isomers and conformations. The greater reactivity of the binary dirhenium acylates in solution, compared to that of the cyclopentadienyl manganese acylate, resulted in a complex reaction mixture. Although the stabilization of hydroxycarbene or hydrido-acyl intermediates of dirhenium carbonyls could not be achieved, their existence in solution was confirmed by the isolation of [(π-H)(2)-(Re(CO)(4){C(O)Fc})(2)] (8), the unique dichloro-bridged biscarbene complex fac-[(π-Cl)(2)-(Re(CO)(3){C(OEt)Fc})(2)] (6), the known hydrido complex [Re(3)(CO)(14)H] (5), the acyl complex [Re(CO)(5){C(O)Fc}] (7), and the aldehyde-functionalized eq-[Re(2)(CO)(9){C(OTiCp(2)Cl)(Fc'CHO)}] (9).

1,3-Bis(2,4,6-trimethyl-phen-yl)-3H-imidazol-1-ium tetra-oxidorhenate(VII).

The title compound, (C(21)H(25)N(2))[ReO(4)], was formed as the unexpected product in an attempted synthesis of a rhenium(I)-N-heterocyclic carbene (NHC) complex. The compound has crystallographic mirror symmetry with both the cation and the tetrahedral anion located across a mirror plane. The cation and anion are linked by a C-H⋯O hydrogen bond.

3-Methyl-anilinium nitrate.

In the title compound, C(7)H(10)N(+)·NO(3) (-), the 3-methyl-anilinium cations inter-act with the nitrate anions through strong bifurcated N(+)-H⋯(O,O) hydrogen bonds, forming a two-dimensional hydrogen-bonded network.

Bis(4-amino-benzoic acid-κN)dichloridozinc(II).

Mol-ecules of the title compound [ZnCl(2)(C(7)H(7)NO(2))(2)], are located on a twofold rotation axis. Two 4-amino-benzoic acid moieties, and two chloride ligands are coordinated to a Zn atom in a tetra-hedral fashion, forming an isolated mol-ecule. Neighbouring mol-ecules are linked through hydrogen-bonded carboxyl groups, as well as N-H⋯Cl hydrogen-bonding inter-actions between amine groups and the chloride ligands of neighbouring mol-ecules, forming a three-dimensional network.

N-(2,4,6-Trimethyl-phen-yl)formamide.

The title compound, C(10)H(13)NO, was obtained as the unexpected, almost exclusive, product in the attempted synthesis of a manganese(I)-N-heterocyclic carbene (NHC) complex. The dihedral angle between the planes of the formamide moiety and the aryl ring is 68.06 (10)°. In the crystal, mol-ecules are linked by N-H⋯O hydrogen bonds, forming infinite chains along the c axis.

The cost of a single concussion in American high school football: a retrospective cohort study.

AIM: The potential financial burden of American football-related concussions (FRC) is unknown. Our objective was to describe the healthcare costs associated with an FRC and determine factors associated with increased costs. METHODOLOGY/RESULTS: A retrospective cohort study of concussed high school football players presenting between November 2017 and March 2020 was undertaken; 144 male high school football players were included. Total costs were about $115,000, for an average direct healthcare cost of $800.10/concussion. Visiting the emergency department (ß = 502.29, 95% CI: 105.79-898.61; p = 0.01), the initial post-concussion symptom scale score (ß = 0.39, 95% CI: 0.11-0.66; p = 0.01) and a post-concussion syndrome diagnosis (ß = 670.37, 95% CI: 98.96-1241.79; p = 0.02) were each independently associated with total costs. CONCLUSION: A granular understanding of cost-driving factors associated with FRC is the first step in understanding the cost-effectiveness of prevention and treatment methods.

Bioactive diterpenes and other constituents of Croton steenkampianus.

A new indanone derivative (1) and two new diterpenoids (2 and 3), together with three known flavonoids, have been isolated from an ethanol extract of the leaves of Croton steenkampianus. The structure of 2 was solved by single-crystal X-ray diffraction analysis, whereas those of 1 and 3 were established mainly by 1D and 2D NMR spectroscopic methods. The isolated compounds were tested for their antiplasmodial activity and cytotoxicity. Antiplasmodial assays against chloroquine-susceptible strains (D10 and D6) and the chloroquine-resistant strains (Dd2 and W2) of Plasmodium falciparum showed that compound 2 gave moderate activities at 9.1-15.8 µM, while none of the compounds were cytotoxic against Vero cells.

Synthesis of heterobimetallic gold(i) ferrocenyl-substituted 1,2,3-triazol-5-ylidene complexes as potential anticancer agents.

1,2,3-Triazol-5-ylidene (trz) complexes of gold(i) containing a ferrocenyl substituent on the C4-position of the trz ring were synthesized to yield the neutral heterobimetallic gold(i) trz chlorido (2), gold(i) trz phenyl (3), and the cationic gold(i) trz triphenylphospine (5) complexes. In order to compare the effect of silver(i) as central metal vs. gold(i), [Ag(trz)2]+ (4) was also prepared, while variation of the C4-1,2,3-triazol-5-ylidene substituent from a ferrocenyl to a phenyl group was done to prepare the monometallic analogue of 5, namely the cationic Au(i) trz triphenylphosphine complex 6. The complexes were characterised with spectroscopic and electrochemical methods, and the single crystal X-ray structures of 2-6 were determined. NMR stability studies of 5 as a representative example of the series of complexes were performed to confirm the stability of the complexes in the solvent dimethylsulfoxide and in aqueous solution. The anti-cancer potential of 5 was evaluated against the lung cancer cell lines A549 and H1975, and the human embryonic kidney cell line (HEK-293) was used as a non-cancer model. IC50 values of 0.89, 0.23 and 5.43 µM, respectively, were obtained for A549, H1975 and HEK-293, respectively, indicating the activity and selectivity of 5 for cancer cells. Fluorescence microscopy experiments as a preliminary mode-of-action study evidenced an apoptotic cell death mechanism rather than necrotic cell death.