Heavier Diferrocenylpnictogenium Ions.

The synthesis, characterization and reactivity of the diferrocenylphosphenium ion [FcP] was extended to the heavier diferrocenylpnictogenium ions, [FcE] (E=As, Sb, Bi). The lighter diferrocenylnitrenium ion, [FcN], was detected by mass spectrometry, but could not be isolated. The molecular structures of [FcE] (E=P, As, Sb, Bi) reveal intramolecular coordination of the iron atoms, which counterbalance the electron deficiency of the pnictogens without affecting the strong Lewis acidities, which were determined according to the method of Gutmann and Beckett.

Synthesis of a stable crystalline nitrene.

Nitrenes are a highly reactive, yet fundamental, compound class. They possess a monovalent nitrogen atom and usually a short life span, typically in the nanosecond range. Here, we report on the synthesis of a stable nitrene by photolysis of the arylazide MFluindN (), which gave rise to the quantitative formation of the arylnitrene MFluindN () (MFluind is dispiro[fluorene-9,3'-(1',1',7',7'-tetramethyl-s-hydrindacen-4'-yl)-5',9''-fluorene]) that remains unchanged for at least 3 days when stored under argon atmosphere at room temperature.

Donor Acceptor Complexes between the Chalcogen Fluorides SF , SeF , SeF and TeF and an N-Heterocyclic Carbene.

The majority of binary chalcogen fluorides are fiercely reactive and extremely difficult to handle. Here, we show that access to crystalline donor-acceptor complexes between chalcogen difluorides (sulfur, selenium) and tetrafluorides (selenium, tellurium) with the N-heterocyclic carbene (NHC) 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) is possible conveniently and safely without the need to generate the highly unstable EF (E=S, Se) or the very toxic and corrosive SeF .

Cationic Carbene Analogues: Donor-Free Phosphenium and Arsenium Ions.

Carbenes and their analogues have constantly enthralled chemists with their intriguing reactivity of ambiphilic character stemming from their electronic structures. Phosphenium and arsenium ions are fiercely reactive cationic species, the stabilization of which has been so far achieved in the condensed phase by dispersing the positive charge through electromeric conjugation with at least one electron-rich substituent (frequently amido groups). Although observed in the gas phase, the isolation of dicoordinate phosphenium and arsenium ions lacking such stabilizing ligands has eluded chemists for decades.

Bulky Polyfluorinated Terphenyldiphenylboranes: Water Tolerant Lewis Acids.

Protocols for the synthesis of the bulky polyfluorinated triarylboranes 2,6-(C F ) C F B(C F ) (1), 2,6-(C F ) C F B[3,5-(CF ) C H ] (2), 2,4,6-(C F ) C H B(C F ) (3), 2,4,6-(C F ) C H B[3,5-(CF ) C H ] (4) were developed. All boranes are water tolerant and according to the Gutmann-Beckett method, 1-3 display Lewis acidities larger than that of the prominent B(C F ) .

Intramolecular Reaction of Transient Phosphenium and Arsenium Ions Giving Rise to Isolable 9-Phospha- and 9-Arsena-Fluorenium Ions.

Transient phosphenium and arsenium ions, generated by fluoride abstraction from bis(m-terphenyl)fluoropnictogens, underwent intramolecular electrophilic attack prior to methyl group migration and gave rise to isolable 9-phospha- and 9-arsena-fluorenium ions.

Taking a snapshot of the triplet excited state of an OLED organometallic luminophore using X-rays.

OLED technology beyond small or expensive devices requires light-emitters, luminophores, based on earth-abundant elements. Understanding and experimental verification of charge transfer in luminophores are needed for this development. An organometallic multicore Cu complex comprising Cu-C and Cu-P bonds represents an underexplored type of luminophore.

A Small Cationic Organo-Copper Cluster as Thermally Robust Highly Photo- and Electroluminescent Material.

Organic light-emitting diodes (OLEDs) are revolutionizing display applications. In this aspect, luminescent complexes of precious metals such as iridium, platinum, or ruthenium still playing a significant role. Emissive compounds of earth-abundant copper with equivalent performance are desired for practical, large-scale applications such as solid-state lighting and displays.

The Bis(ferrocenyl)phosphenium Ion Revisited.

The bis(ferrocenyl)phosphenium ion, [Fc P] , reported by Cowley et al. (J. Am.

Tri- and Tetranuclear Metal-String Complexes with Metallophilic d -d Interactions.

The reaction of 2,6-F C H SiMe with Ph PLi provided 2,6-(Ph P) C H SiMe (1), which can be regarded as precursor for the novel anionic tridentate ligand [2,6-(Ph P) C H ] (PCP) . The reaction of 1 with [AuCl(tht)] (tht=tetrahydrothiophene) afforded 2,6-(Ph PAuCl) C H SiMe (2). The subsequent reaction of 2 with CsF proceeded with elimination of Me SiF and yielded the neutral tetranuclear complex linear-[Au Cl (PCP) ] (3) comprising a string-like arrangement of four Au atoms.

Transient Phosphenium and Arsenium Ions versus Stable Stibenium and Bismuthenium Ions.

Fluoride abstraction from bis-m-terphenylelement fluorides (2,6-Mes C H ) EF (E=P, As) generated the highly reactive phosphenium ion [(2,6-Mes C H ) P] and the arsenium ion [(2,6-Mes C H ) As] , which immediately underwent intramolecular electrophilic substitution and formation of an 1,2,4-trimethyl-6-mesityl-5-m-terphenyl-benzo[b]phospholium ion and an 1,2,4-trimethyl-6-mesityl-5-m-terphenyl-benzo[b]arsolium ion, respectively. The formation of the latter involved a methyl group migration from the ortho-position of a flanking mesityl group to the meta-position. This reactivity of [(2,6-Mes C H ) E] (E=P, As) is in sharp contrast to the related stibenium ion [(2,6-Mes C H ) Sb] and bismuthenium ion [(2,6-Mes C H ) Bi] , which have been recently isolated and fully characterized (Angew.

Functionalized Fluorophosphonium Ions.

Efforts to prepare an elusive donor-free phosphenium ion, [R P] , led us to synthesize functionalized fluorophosphonium cations of the type [R P(F)X] (X=SiEt , H, F), which were obtained from the related neutral fluorophosphines R PF and R PF upon protonation and reaction with solvated [Et Si] ions (R=2,6-Mes C H ). The hypothetical reductive elimination of [R P(F)SiEt ] and [R P(F)H] affording [R P] , Et SiF and HF, respectively, was calculated to be endothermic by 40.1 and 190.

Transmetallation of bis(6-diphenylphosphinoxy-acenapth-5-yl)mercury with tin tetrachloride, antimony trichloride and bismuth trichloride.

We recently communicated (Angew. Chem. Int.

Heavy Carbene Analogues: Donor-Free Bismuthenium and Stibenium Ions.

Kinetically stabilized congeners of carbenes, R C, possessing six valence electrons (four bonding electrons and two non-bonding electrons) have been restricted to Group 14 elements, R E (E=Si, Ge, Sn, Pb; R=alkyl or aryl) whereas isoelectronic Group 15 cations, divalent species of type [R E] (E=P, As, Sb, Bi; R=alkyl or aryl), were unknown. Herein, we report the first two examples, namely the bismuthenium ion [(2,6-Mes C H ) Bi][BAr ] (1; Mes=2,4,6-Me C H , Ar =3,5-(CF ) C H ) and the stibenium ion [(2,6-Mes C H ) Sb][B(C F ) ] (2), which were obtained by using a combination of bulky meta-terphenyl substituents and weakly coordinating anions.

A Monoaryllead Trichloride That Resists Reductive Elimination.

Transmetallation of Pb(OAc) with R Hg (1), followed by treatment with HCl in Et O, provided RPbCl (2), the first kinetically stabilized monoorganolead trihalide that resists reductive elimination under ambient conditions. The kinetic stabilisation relies on an intramolecularly coordinating O-donor substituent (R=6-Ph P(O)-Ace-5-). The gram-scale preparation of 2 was key for the synthesis of unsymmetrically substituted diaryllead dichlorides RR'PbCl (3 a, R'=Ph; 3 b, R'=4-MeOC H ; 3 c, R'=4-Me NC H ).

The Weakly Coordinating Tris(trichlorosilyl)silyl Anion.

Closely following the procedure for the preparation of the base-stabilized dichlorosilylene complex NHC ⋅SiCl reported by Roesky, Stalke, and co-workers (Angew. Chem. Int.

Mapping the Trajectory of Nucleophilic Substitution at Silicon Using a peri-Substituted Acenaphthyl Scaffold.

The second-order nucleophilic substitution (S 2) reaction at a silicon atom is scrutinized by means of snapshots along a pseudoreaction coordinate. Phosphine and fluoride represent both attacking and leaving groups in the modeled S 2 reaction. In the experimentally obtained 5-diphenylphosphinoacenaphth-6-yl-dimethylfluorosilane, 1, the phosphine and fluorosilane moieties are forced into immediate proximity through an acenaphthyl scaffold, that is, they exhibit peri interactions that serve as the model of the reactant ion-molecule complex and starting point for a theoretical potential-energy surface (PES) scan.

Correction: The CARD9 Polymorphisms rs4077515, rs10870077 and rs10781499 Are Uncoupled from Susceptibility to and Severity of Pulmonary Tuberculosis.

[This corrects the article DOI: 10.1371/journal.pone.

The CARD9 Polymorphisms rs4077515, rs10870077 and rs10781499 Are Uncoupled from Susceptibility to and Severity of Pulmonary Tuberculosis.

Genetic variants in the CARD9 gene predispose to inflammatory disorders and chronic infectious diseases. Tuberculosis (TB), a chronic infectious disease affecting the lung, is lethal in Card9-deficient mice. We hypothesized that polymorphisms in the CARD9 gene influence TB progression and disease-associated lung damage in humans.

Mixed triorganobismuthines RAr2Bi [Ar = C6F5, 2,4,6-(C6F5)3C6H2] and hypervalent racemic Bi-chiral diorganobismuth(iii) bromides RArBiBr (Ar = C6F5, Mes, Ph) with the ligand R = 2-(Me2NCH2)C6H4. Influences of the organic substituent.

Triorganobismuthines R(C6F5)2Bi (1) and R[2,4,6-(C6F5)3C6H2]2Bi (2) [R = 2-(Me2NCH2)C6H4] were synthesized by reaction of RBiBr2 with C6F5MgBr and 2,4,6-(C6F5)3C6H2Li, respectively, in a 1 : 2 molar ratio. The Bi-chiral bromides R(C6F5)BiBr (3), R(Mes)BiBr (4), and R(Ph)BiBr (5) were obtained from RBiBr2 and C6F5MgBr, MesMgBr or PhMgBr, or from PhBiBr2 and RLi, in a 1 : 1 molar ratio. The molecular structures of 1-5 were determined by single-crystal X-ray diffraction and are discussed taking into account the chirality of the species.

Morphological aspects in tuberculosis of oral cavity - our experience and a review of the literature attempt.

Aim: The authors continue a started series of articles about extrapulmonary tuberculosis (EPTB) with the assessment of the mycobacterial lesions discovered on tissue samples of the oral cavity structures in the Department of Pathology of the Emergency County Hospital of Craiova, Romania, and the review of the cases reported in the literature available, between 1990 and 2013.

Materials And Methods: The studied material consisted, for our series, of samples obtained by biopsy or surgical excision, including the salivary glands and excluding the lymph nodes from 17 patients histopathologically diagnosed with tuberculosis and, for review series, 190 papers selected from PubMed database.

Results: The number of cases reported increased throughout the studied period.

Lymph node tuberculosis - an attempt of clinico-morphological study and review of the literature.

Aim: The authors assessed the mycobacterial lesions in the lymph nodes discovered on tissue samples coming from the surgical stage in the Department of Pathology, Emergency County Hospital of Craiova, Romania, starting from 1990 until 2012.

Materials And Methods: The studied material consisted of lymph node (LN) tissue samples obtained by biopsy or surgical excision from 362 patients histopathologically diagnosed with tuberculosis. For confirming the diagnosis, Ziehl-Neelsen staining was carried out and, in some cases, PCR technique was used.

(2,4,6-Trimethyl-phen-yl)boronic acid-triphenyl-phosphine oxide (1/1).

In the crystal structure of the title compound, C(9)H(13)BO(2)·C(18)H(15)OP, there are O-H⋯O hydrogen bonds between the O atom of triphenyl-phosphine oxide and one hy-droxy group of the boronic acid. Boronic acid mol-ecules form inversion-related hydrogen-bonded dimers in an R(2) (2)(8) motif. The structure is consolidated by inter-molecular C-H⋯O bonds and C-H⋯π inter-actions.

3,5-Dibromo-2',3',4',5',6'-penta-methyl-1,1'-biphen-yl.

In the crystal structure of the title compound, C(17)H(18)Br(2), the benzene rings are almost perpendicular [dihedral angle = 84.0 (3)°]. The crystal structure is consolidated by the presence of C-Br⋯π inter-actions.

2'-Iodo-2,2'',3,3'',4,4'',5,5'',6,6''-deca-methyl-1,1':3',1''-terphenyl chloro-form monosolvate.

The title compound, C(28)H(33)I·CHCl(3), forms dimers through C-I⋯π inter-actions. The crystal structure is consolidated by the presence of C-H⋯π inter-actions between the chloro-form solvent and the main mol-ecule.