Controlled Ring Opening of a Tetracyclic Tetraphosphane with Twofold Metallocene Bridging.

A direct route to a doubly ferrocene bridged tetracyclic tetraphosphane 1 was developed via reductive coupling of Fe(CpPCl2)2 (2 a), where a chlorine terminated linear P4-compound 3 could be identified as an intermediate. Selective P-P bond activation was further achieved by reacting 1 with elemental selenium or [Cp*Al]4, where regioselective insertion of Se or Al atoms resulted in ferrocenylene bridged [P4Se] (4) or [P4Al] (7) moieties. Compound 7 can be transformed to a hydrogen terminated linear P4 species, 8, with protic solvents. Methylation of compound 1 with MeOTf, proceeds via intermediate formation of monomethylated species 5, which gradually produced Me2-terminated dicationic 6, again containing a linear P4-unit. Besides spectroscopic characterization, the structural details of compounds 1, 4, 6, and 8 could be determined by SC-XRD. Moreover, DFT calculations were used to rationalize the reactivity of 1, derived compounds and intermediates. As a key feature, 1 undergoes ring opening polymerization to a linear polyphosphane 9.

Explanatory power by vagueness. Challenges to the strong prior hypothesis on hallucinations exemplified by the Charles-Bonnet-Syndrome.

Predictive processing models are often ascribed a certain generality in conceptually unifying the relationships between perception, action, and cognition or the potential to posit a 'grand unified theory' of the mind. The limitations of this unification can be seen when these models are applied to specific cognitive phenomena or phenomenal consciousness. Our article discusses these shortcomings for predictive processing models of hallucinations by the example of the Charles-Bonnet-Syndrome. This case study shows that the current predictive processing account omits essential characteristics of stimulus-independent perception in general, which has critical phenomenological implications. We argue that the most popular predictive processing model of hallucinatory conditions - the strong prior hypothesis - fails to fully account for the characteristics of nonveridical perceptual experiences associated with Charles-Bonnet-Syndrome. To fill this explanatory gap, we propose that the strong prior hypothesis needs to include reality monitoring to apply to more than just veridical percepts.

A General Strategy for Increasing the Air Stability of Phosphines Including Primary Phosphines.

A general approach for increasing the air-stability of various primary phosphines in the absence of kinetic stabilization is presented that contrasts with previous interpretations, which were limited to specific phosphines. This contribution shows the synthesis of a series of air-stable primary phosphines Fc(CH2 )n PH2 , where n=0,1,2,3; and Fc=ferrocenyl, and their corresponding isolable primary phosphine oxides. It was demonstrated that the ferrocene moiety exerts an antioxidant effect on the primary phosphine group, which is intermolecular, solvent dependent and increases with the electron density on the ferrocene moiety. Furthermore, we demonstrated that the presence of ferrocene in solution also inhibits the oxidation of other secondary and tertiary phosphines in air. Together our findings suggest that quenching of singlet oxygen is the actual reason for the antioxidant effect; this was experimentally confirmed by using other established singlet oxygen quenchers, thus demonstrating a key role of singlet oxygen in the aerobic oxidation of phosphines.

Gradual Donor Stabilization of a Transient Ferrocene Bridged Bisphosphanyl Phosphenium Cation.

A transient phosphenium cation embedded into a [3]ferrocenophane scaffold was formed via chloride abstraction. The cation has been trapped with phosphane, carbene, and silylene donors resulting in stable adducts or bond activation of the ferrocenophane bridge. In the absence of donors, dimerization of the phosphenium cation to the corresponding dication is observed or P-C bond activation with migration of a substituent leading to a putative phosphoniodiphosphene. Using 1,3-di-tert-butylimidazol-2-silylene as the donor, further reaction of the initially formed chlorosilane leads to activation of a P-P bond of the ferrocenophane scaffold with ring expansion of the ansa-bridge. The donor formation and bonding situation are investigated by density functional theory calculations as well as experimental methods (e.g., NMR spectroscopy and X-ray crystallography).

Chalcogen-Transfer Rearrangement: Exploring Inter- versus Intramolecular P-P Bond Activation.

Invited for the cover of this issue are Rudolf Pietschnig and co-workers at the University of Kassel and Zsolt Kelemen at Budapest University of Technology and Economics. The image depicts Selene, the goddess of the moon in ancient Greek mythology, and the cycle of chalcogen-transfer rearrangement in the starry sky over the hills of the mountainous region of the northern shore of Lake Balaton (Mts. Badacsony and Gulács) in Hungary. Read the full text of the article at 10.1002/chem.202002481.

Chalcogen-Transfer Rearrangement: Exploring Inter- versus Intramolecular P-P Bond Activation.

tert-Butyl-substituted diphospha[2]ferrocenophane has been used as a stereochemically confined diphosphane to explore the addition of O, S, Se and Te. Although the diphosphanylchalcogane has been obtained for tellurium, all other chalcogens give diphosphane monochalcogenides. The latter transform via chalcogen-transfer rearrangement to the corresponding diphosphanylchalcoganes upon heating. The kinetics of this rearrangement has been followed with NMR spectroscopy supported by DFT calculations. Intermediates during rearrangement point to a disproportionation/synproportionation mechanism for the S and Se derivatives. Cyclic voltammetry together with DFT studies indicate ferrocene-centred oxidation for most of the compounds presented.

C2-Symmetric P-Stereogenic Ferrocene Ligands with Heavier Chalcogenophosphinous Acid Ester Donor Sites.

tert-Butyl-substituted diphospha[2]ferrocenophane was used as a stereochemically confined diphosphane to investigate the addition of various dichalcoganes (R2Ch2; Ch = S, Se, Te and R = Me, Ph). Bischalcogenophosphinous acid esters bearing four soft donor sides were obtained as a mixture of rac and meso diastereomers and characterized by means of multinuclear NMR and X-ray analysis. The coordination chemistry of multidentate ligand 3b was explored toward d10 coinage metal centers (Cu(I), Ag(I), and Au(I)), yielding various bimetallic complexes.

Gradual Coordination and Reversible P-P Bond Activation of a P3 -Unit with Transition Metal Carbonyls.

Coordination of a stereochemically defined P3 -chain to a series of transition metal carbonyls [M(CO)x ]z- (M = Mn (x = 5, z = 1), Fe (x = 4, z = 2) or Co (x = 4, z = 1)) is explored using a [3]ferrocenophane scaffold. A gradual transition from η1 -, η2 - to Î·3 -coordination is observed where in the η2 -mode the terminal positions of the phosphorus chain are bridged. With an excess of cobalt carbonyl successive P-P bond activation and gradual separation of the central phosphorus atoms from the phosphorus chain has been observed. This process is reversible and with suitable reagents such as methyl lithium, the P3 -unit is regenerated in stereospecific manner. The bonding situation and steps of the gradual P-P bond activation are investigated by DFT calculations as well as experimental methods (e.g., NMR spectroscopy, X-ray crystallography).

At the limits of bisphosphonio-substituted stannylenes.

Donor stabilization of Sn(II) and Pb(II) halides with 1,1'-ferrocenylene bridged bisphosphanes has been explored for Fe(C5 H4 P(C6 H5 )2 )2 (dppf), and Fe(C5 H4 PH(C4 H9 ))2 . These bisphosphanes are reacted with SnBr2 and PbCl2 with and without additional Lewis acid (AlCl3 ) forming acyclic and cyclic donor adducts from which the latter represent bisphosphoniotetrylenes. Since dynamic exchange in solution is observed, characterization includes solution and solid-state NMR in addition to SC-XRD, amended by DFT calculations.

Screening for Resistant Bacteria, Antimicrobial Resistance Genes, Sexually Transmitted Infections and Schistosoma spp. in Tissue Samples from Predominantly Vaginally Delivered Placentae in Ivory Coast and Ghana.

Medical complications during pregnancy have been frequently reported from Western Africa with a particular importance of infectious complications. Placental tissue can either become the target of infectious agents itself, such as, e.g., in the case of urogenital schistosomiasis, or be subjected to contamination with colonizing or infection-associated microorganisms of the cervix or the vagina during vaginal delivery. In the retrospective cross-sectional assessment presented here, the quantitative dimension of infection or colonization with selected resistant or pathogenic bacteria and parasites was regionally assessed. To do so, 274 collected placental tissues from Ivory Coastal and Ghanaian women were subjected to selective growth of resistant bacteria, as well as to molecular screening for beta-lactamase genes, Schistosoma spp. and selected bacterial causative agents of sexually transmitted infections (STI). Panton-Valentine-negative methicillin-resistant Staphylococcus aureus (MRSA) was grown from 1.8% of the tissue samples, comprising the spa types t008 and t688, as well as the newly detected ones, t12101 (n = 2) and t12102. While the culture-based recovery of resistant Enterobacterales and nonfermentative rod-shaped Gram-negative bacteria failed, molecular assessments confirmed beta-lactamase genes in 31.0% of the samples with multiple detections of up to four resistance genes per sample and blaCTX-M, blaIMP, blaGES, blaVIM, blaOXA-58-like, blaNDM, blaOXA-23-like, blaOXA-48-like and blaKPC occurring in descending order of frequency. The beta-lactamase genes blaOXA-40/24-like, blaNMC_A/IMI, blaBIC, blaSME, blaGIM and blaDIM were not detected. DNA of the urogenital schistosomiasis-associated Schistosoma haematobium complex was recorded in 18.6% of the samples, but only a single positive signal for S. mansoni with a high cycle-threshold value in real-time PCR was found. Of note, higher rates of schistosomiasis were observed in Ghana (54.9% vs. 10.3% in Ivory Coast) and Cesarean section was much more frequent in schistosomiasis patients (61.9% vs. 14.8% in women without Schistosoma spp. DNA in the placenta). Nucleic acid sequences of nonlymphogranuloma-venereum-associated Chlamydia trachomatis and of Neisseria gonorrhoeae were recorded in 1.1% and 1.9% of the samples, respectively, while molecular attempts to diagnose Treponema pallidum and Mycoplasma genitalium did not lead to positive results. Molecular detection of Schistosoma spp. or STI-associated pathogens was only exceptionally associated with multiple resistance gene detections in the same sample, suggesting epidemiological distinctness. In conclusion, the assessment confirmed considerable prevalence of urogenital schistosomiasis and resistant bacterial colonization, as well as a regionally expected abundance of STI-associated pathogens. Continuous screening offers seem advisable to minimize the risks for the pregnant women and their newborns.