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A series of xylene charge-transfer complexes with fluorine-substituted tetracyanoquinodimethane (TCNQ) acceptors were studied experimentally and theoretically in order to reveal the role of various intermolecular interactions on stoichiometry and the crystal structure. It was shown that o-xylene face-to-face donor–donor interactions became significant enough to result in the formation of 2:1 cocrystals with F1TCNQ and F4TCNQ irrespective of growth conditions. The supramolecular arrangement in these cocrystals is mainly determined by the number of fluorine atoms in the acceptor. Comparative DFT and MP2 calculations of the pairwise intermolecular interactions revealed the overestimation of the dispersion energy for these systems by the DFT-wB97XD approach. [ABSTRACT FROM AUTHOR]

This paper illustrates how the size and type of substituent R in the phosphinate group of ferrocenyl bisphosphinic acids can affect conformational possibilities and coordination packing. It also demonstrates that H-phosphinate plays a key role in variational mobility, while Me- or Ph- substituents of the phosphinate group can only lead to 0D complexes or 1D coordination polymer. Overall, this paper provides valuable insights into the design and construction of coordination polymers based on ferrocene-contained linkers. It sheds light on how different reaction conditions and substituents can affect conformational possibilities and coordination packing, which could have significant implications for developing new polymers with unique properties. [ABSTRACT FROM AUTHOR]

The iron‐catalyzed oxidative C−C homocoupling of diarylamines affords 2,2′‐bis(arylamino)‐1,1′‐biaryls which represent crucial synthetic building blocks for an access to a range of seven‐membered heterocyclic ring systems. Reaction with paraformaldehyde, diphenyl carbonate, and diphenyl sulfite as efficient 1,1‐dielectrophiles led to dibenzo[d,f][1,3]diazepines, dibenzo[d,f][1,3]diazepinones, and dibenzo[c,e][1,2,7]thiadiazepine 6‐oxides. The synthetic procedures enable short and practical routes to these 1,3‐diazepine derivatives under mild reaction conditions and with a high tolerance of various functional groups. [ABSTRACT FROM AUTHOR]

The article discusses the impact of modern technologies on a person's lifeworld: the anthropological transformations generated by large-scale digitalisation and virtualisation. The goal is to understand the specifics of modern technologies' impact on a person and their lifeworld. Three groups of problems are analysed. The first group is related to the replacement of the real being by the virtual (the concept of 'subontology'), to the identification of the effect of superdetermination by the virtual. The second one is aimed at analysing technological rationality. The third group involves the consideration of the virtual person phenomenon and its distinctive features. The methodological basis is the principle of sociocultural determination. It allows us to identify 1) the impact of the modern digital era on the lifeworld and 2) anthropological shifts that form a new type of person. The authors conclude that the subontology generated by digital algorithms and network interactions sets the suprapersonal scale of control. The new type of person is characterised by the presence of 'digital skills.' In the current situation, the boundaries between the real and the virtual are blurring. Socio-humanitarian reflection reveals and makes it possible to comprehend the negative consequences of the virtualisation of the lifeworld. [ABSTRACT FROM AUTHOR]

We describe an iron‐catalyzed asymmetric oxidative C−C coupling of diarylamines which proceeds at room temperature with air as final oxidant. Using hexadecafluorophthalocyanine‐iron(II) as catalyst in the presence of catalytic amounts of an axially chiral biaryl phosphoric acid, the resulting chiral 2,2′‐diamino‐1,1′‐biaryls are obtained in up to 90 % ee as confirmed by chiral HPLC. A detailed mechanism has been proposed with a radical cation‐chiral phosphate ion pair as key intermediate leading to the observed asymmetric induction. [ABSTRACT FROM AUTHOR]

A coordination polymer has been synthesized using ferrocene-based ligand-bearing phosphinic groups of 1,1′-ferrocene-diyl-bis(H-phosphinic acid)), and samarium (III). The coordination polymer's structure was studied by both single-crystal and powder XRD, TG, IR, and Raman analyses. For the first time, the Mössbauer effect studies were performed on ferrocenyl phosphinate and the polymer based on it. Additionally, the obtained polymer was studied by the method of cyclic and differential pulse voltammetry. It is shown that it has the most positive potential known among ferrocenyl phosphinate-based coordination polymers and metal–organic frameworks. Using the values of the oxidation potential, the polymer was oxidized and the ESR method verified the oxidized Fe(III) form in the solid state. Additionally, the effect of the size of the phosphorus atom substituent of the phosphinate group on the dimension of the resulting coordination compounds is shown. [ABSTRACT FROM AUTHOR]

The relative configuration of the marine sesquiterpenoid oxyfungiformin, isolated from the soft coral Capnella fungiformis, was confirmed by synthesis using the natural product guaiol as chiral precursor. The absolute configuration of oxyfungiformin could be assigned by combination of X‐ray diffraction and comparison of the values for the specific optical rotation. Oxyfungiformin and a diastereoisomer showed cytotoxic activity in cells originating from cancers of the lung, breast, and cervix. [ABSTRACT FROM AUTHOR]

The synthetic route to the manufacture of bifunctional zirconocene/borane complex is described. This complex was characterized by X-ray diffraction method.

Gas phase structure and vibrational spectrum of tetrabromothiophene were calculated by ab initio methods. The unusual fit proved from solid phase Raman spectrum and the compounds' solidification into very small, irregularly arranged crystallites is correlated to the screening of the thiophene moiety by the bromine atoms.

We describe the oxygenation of tertiary arylamines, and the amination of tertiary arylamines and phenols. The key step of these coupling reactions is an iron‐catalyzed oxidative C−O or C−N bond formation which generally provides the corresponding products in high yields and with excellent regioselectivity. The transformations are accomplished using hexadecafluorophthalocyanine−iron(II) (FePcF16) as catalyst in the presence of an acid or a base additive and require only ambient air as sole oxidant. [ABSTRACT FROM AUTHOR]

Herein, we describe a convenient and general method for the oxidation of olefins to ketones using either tris(dibenzoylmethanato)iron(III) [Fe(dbm)3] or a combination of iron(II) chloride and neocuproine (2,9‐dimethyl‐1,10‐phenanthroline) as catalysts and phenylsilane (PhSiH3) as additive. All reactions proceed efficiently at room temperature using air as sole oxidant. This transformation has been applied to a variety of substrates, is operationally simple, proceeds under mild reaction conditions, and shows a high functional‐group tolerance. The ketones are formed smoothly in up to 97 % yield and with 100 % regioselectivity, while the corresponding alcohols were observed as by‐products. Labeling experiments showed that an incorporated hydrogen atom originates from the phenylsilane. The oxygen atom of the ketone as well as of the alcohol derives from the ambient atmosphere. [ABSTRACT FROM AUTHOR]

Mononuclear and polymeric Co(II) complexes were obtained with enantiopure and racemic N-thiophosphorylated thioureas with a metal to ligand ratio of 1 : 2. To control the stereochemistry of the complexes synthesized from racemic ligands, pyridine and pyrazine were used as co-ligands, the latter bridging cobalt ions in 1D-coordination polymers. Single crystal X-ray diffraction shows that 1D and 2D supramolecular homochiral arrangements in racemic crystals of mononuclear complexes are transferred to their polymeric counterparts. The cobalt oxidation state in coordination polymers was proved by electrochemistry. Magnetization and ESR measurements reveal a typical magnetic behavior of Co(II) metal ions in a distorted octahedral coordination. The polymeric crystals start to lose crystallinity from the surface at 65 °C, the process being accompanied with a color change and the evolution of gas. The ESR spectrum reduces in intensity after sample heating, tentatively, due to the smearing of the ESR response from the amorphous part of the sample. [ABSTRACT FROM AUTHOR]

Here, the first example of phosphinic acid containing Ugi's amine (HL) is presented. Utilization of this phosphinic acid as a ligand along with 4,4′-bipyridine (bpy) facilitated the synthesis of the first coordination polymer based on Ugi's amine with the composition Ni(bpy)2L2. The crystal structure of both ligand and polymer were solved from the single-crystal X-ray diffraction data. The acid exists as zwitterion and crystallizes as a mixture of two racemic forms. The coordination polymer comprises layers composed of Ni(bipy)2, terminated by L as monodentate ligands, coordinated to Ni through the phosphinate group. The solid-state cyclic voltammetry was used as an analytical tool, which made it possible to estimate the iron to nickel ratio in the structure of coordination polymer. The cathodic shift of the oxidation potential of the ferrocene fragment in the polymer in comparison to free acid demonstrates a strong interaction of iron and nickel within the coordination polymer structure. [ABSTRACT FROM AUTHOR]

We describe the first total synthesis of the recently discovered pyrano[3,2- a ]carbazole alkaloid clausenalansine A. The synthetic strategy for the construction of this formylpyrano[3,2- a ]carbazole is based on a sequence of Buchwald–Hartwig coupling, palladium(II)-catalyzed oxidative cyclization, Lewis acid promoted annulation of the pyran ring, and chemoselective oxidation of a methyl to a formyl group. [ABSTRACT FROM AUTHOR]