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Chiral organic molecules possessing high quantum yields, circular dichroism, and circularly polarized luminescence values have great potential as optically active materials for future applications. Recently, the identification of a promising class of inherently chiral compounds was reported, namely macrocyclic 1,3‐butadiyne‐linked pseudo‐meta[2.2]paracyclophanes, displaying high circular dichroism and related gabs values albeit modest quantum yields. Increasing the quantum yields in an attempt to get bright circularly polarized light emitters, the high‐yielding heterocyclization of those 1,3‐butadiyne bridges resulting in macrocyclic 2,5‐thienyls‐linked pseudo‐meta [2.2]paracyclophanes is herein described. The chiroptical properties of both, the previously reported 1,3‐butadiyne, and the novel 2,5‐thienyl bridged macrocycles of various sizes, are experimentally recorded, and theoretically described using density‐functional theory. [ABSTRACT FROM AUTHOR]

The exploration of new materials is timeless. Especially 2D‐materials have gotten much interest in the last decades. This work proposes a new route towards a fascinating class of 2D materials: molecular textiles. The suggested bottom‐up approach focuses on the 2D self‐assembly of a cross‐shaped monomer at the water/air interface. A 3D cross‐shaped motive was designed, synthesized, and characterized, which exhibits the required structural features, i. e., static and dynamic control. Analysis of the cross‐shaped motive by 1H‐NMR spectroscopy, X‐ray structure, and chiral stationary phase HPLC proved the rigidity and stability of the system, and thus also its potential for the here suggested new strategy towards molecular textiles. Three variants of a Schiff‐base precursor pair functionalized monomer were synthesized and characterized by 1H‐NMR spectroscopy, 13C‐NMR spectroscopy, and mass spectrometry. Finally, the network formation of the monomer is shown to be triggered by deprotonation of its ammonium salt, corroborated with FT‐IR analysis. [ABSTRACT FROM AUTHOR]

Orthogonal joints, understood as connections with an angle of 90°, were introduced in the design of the "Geländer" model compounds 1 and 2. The banister, consisting of a conjugated carbazole dimer linked by either 1,3‐butadiyne (2) or a single thiophene (1), wraps around an axis composed of a phthalimide dimer due to the dimensional mismatch of both subunits, which are interconnected by phenylene rungs. The "Geländer" structure was assembled from a monomer comprising the 1,4‐diaminobenzene rung with one amino substituent as part of a 4‐bromo phthalimide subunit forming the orthogonal junction to the axis, and the other as part of a masked 2‐ethynyl carbazole as orthogonal joint to the banister. The macrocycle was obtained by two sequential homocoupling steps. A first dimerization by a reductive homocoupling assembled the axis, while an oxidative acetylene coupling served as ring‐closing reaction. The formed butadiyne was further derivatized to a thiophene, rendering all carbons of the model compound sp2 hybridized. Both helical structures were fully characterized and chirally resolved. Assignment of the enantiomers was achieved by simulation of chiroptical properties and enantiopure synthesis. [ABSTRACT FROM AUTHOR]

The synthetic access to macrocyclic molecular topologies with interesting photophysical properties has greatly improved thanks to the successful implementation of organic and inorganic corner units. Based on recent reports, we realized that pseudo‐meta [2.2]paracyclophanes (PCPs) might serve as optimal corner units for constructing 3D functional materials, owing to their efficient electronic communication, angled substituents and planar chirality. Herein, we report the synthesis, characterization and optical properties of four novel all‐carbon enantiopure macrocycles bearing three to six pseudo‐meta PCPs linked by 1,3‐butadiyne units. The macrocycles were obtained by a single step from enantiopure, literature‐known dialkyne pseudo‐meta PCP and were unambiguously identified and characterized by state of the art spectroscopic methods and in part even by x‐ray crystallography. By comparing the optical properties to relevant reference compounds, it is shown that the pseudo‐meta PCP subunit effectively elongates the conjugated system throughout the macrocyclic backbone, such that already the smallest macrocycle consisting of only three subunits reaches a polymer‐like conjugation length. Additionally, it is shown that the chiral pseudo‐meta PCPs induce a remarkable chiroptical response in the respective macrocycles, reaching unprecedented high molar circular dichroism values for all‐carbon macrocycles of up to 1307 L mol−1 cm−1. [ABSTRACT FROM AUTHOR]

Two silyl [P,Si]‐chelate cobalt hydrides, [(o‐Si(Ph)2‐(PiPr2)C6H4)Co(H)(PMe3)2] (1) and [(o‐Si(Ph)2‐(PPh2)C6H4)Co(H)(PMe3)2] (2), were prepared through the chelate‐assisted Si–H activation of bidentate preligand, o‐HSi(Ph)2‐(PiPr2)C6H4 (L1) and o‐HSi(Ph)2‐(PPh2)C6H4 (L2) by [Co(PMe3)4] or [Co(Me)(PMe3)4], respectively. Both cobalt(II) hydrides 1 and 2 can efficiently catalyze hydrosilylation of olefins, and the catalytic effect of complex 1 is better than that of complex 2. The Markovnikov products were formed from aryl alkenes, whereas the anti‐Markovnikov products were produced from aliphatic alkenes. In the mechanism study, a silyl cobalt(II) intermediate, [(o‐Si(Ph)2‐(PiPr2)C6H4)Co(SiHPh2)(PMe3)2], as the real catalyst is proposed and supported by in situ infrared (IR) study. The molecular structure of complex 1 was determined by single crystal X‐ray diffraction analysis. [ABSTRACT FROM AUTHOR]

The design and creation of soft porous crystals combining regularity and flexibility may promote potential applications for gas storage and separation due to their deformable framework's responsiveness to external stimuli. The flexibility of metal–organic frameworks (MOFs) relies on alterable degrees of freedom that are mainly provided by organic linkers or the junctions linking organic and inorganic building units. Herein, we report a new dynamic MOF whose flexibility originates from an unprecedented tailorable Mn8O38‐cluster and shows simultaneous coordination geometry changes and ligand migration that are reversibly driven by guest exchange. This provides an extra degree of freedom to the framework's deformation, resulting in three‐dimensional variations in the framework that subtly respond to varied aromatic molecules. The gas adsorption behavior of this flexible MOF was evaluated, and the selective separation of light hydrocarbons and Freon gases is achieved. [ABSTRACT FROM AUTHOR]

The design and creation of soft porous crystals combining regularity and flexibility may promote potential applications for gas storage and separation due to their deformable framework's responsiveness to external stimuli. The flexibility of metal–organic frameworks (MOFs) relies on alterable degrees of freedom that are mainly provided by organic linkers or the junctions linking organic and inorganic building units. Herein, we report a new dynamic MOF whose flexibility originates from an unprecedented tailorable Mn8O38‐cluster and shows simultaneous coordination geometry changes and ligand migration that are reversibly driven by guest exchange. This provides an extra degree of freedom to the framework's deformation, resulting in three‐dimensional variations in the framework that subtly respond to varied aromatic molecules. The gas adsorption behavior of this flexible MOF was evaluated, and the selective separation of light hydrocarbons and Freon gases is achieved. [ABSTRACT FROM AUTHOR]

Two derivatives, 3 L and 9 L, of a ditopic, multiply hydrogen-bonding molecule, known for more than a decade, have been found, in the solid state as well as in solvents of low polarity at room temperature, to exist not as monomers, but to undergo a remarkable self-assembly into a complex supramolecular species. The solid-state molecular structure of 3 L, determined by single-crystal X-ray crystallography, revealed that it forms a highly organized hexameric entity 3 L6 with a capsular shape, resulting from the interlocking of two sets of three monomolecular components, linked through hydrogen-bonding interactions. The complicated 1H NMR spectra observed in o-dichlorobenzene ( o-DCB) for 3 L and 9 L are consistent with the presence of a hexamer of D3 symmetry in both cases. DOSY measurements confirm the hexameric constitution in solution. In contrast, in a hydrogen-bond-disrupting solvent, such as DMSO, the 1H NMR spectra are very simple and consistent with the presence of isolated monomers only. Extensive temperature-dependent 1H NMR studies in o-DCB showed that the L6 species dissociated progressively into the monomeric unit on increasing th temperature, up to complete dissociation at about 90 °C. The coexistence of the hexamer and the monomer indicated that exchange was slow on the NMR timescale. Remarkably, no species other than hexamer and monomer were detected in the equilibrating mixtures. The relative amounts of each entity showed a reversible sigmoidal variation with temperature, indicating that the assembly proceeded with positive cooperativity. A full thermodynamic analysis has been applied to the data. [ABSTRACT FROM AUTHOR]

A novel silylene supported iron hydride [Si, C]FeH (PMe3)3 (1) was synthesized by C (sp3)‐H bond activation with zero‐valent iron complex Fe (PMe3)4. Complex 1 was fully characterized by spectroscopic methods and single crystal X‐ray diffraction analysis. To the best of our knowledge, 1 is the first example of silylene‐based hydrido chelate iron complex produced through activation of the C (sp3)−H bond. It was found that complex 1 exhibited excellent catalytic activity for hydrosilylation of aldehydes and ketones. The catalytic system showed good tolerance and catalytic activity for the substrates with different functional groups on the benzene ring. It is worth mentioning that, the experimental results showed that both ketones and aldehydes could be reduced in good to excellent yields under the same catalytic conditions. Based on the experiments and literature reports, a possible catalytic mechanism was proposed. [ABSTRACT FROM AUTHOR]

Studies the crystal structure of acetonitrile[2,6-bis(pyrazol-1-y)pyridine](isonicotinamide) copper(II) cation. Conformation of the pyridine ring of the isonicotinamide ligand; Structural parameters of the hydrogen-bonded contacts.

The dehydration of primary amides to their corresponding nitriles using four [PSiP]‐pincer hydrido iron complexes 1–4 [(2‐Ph2PC6H4)2MeSiFe(H)(PMe3)2 (1), (2‐Ph2PC6H4)2HSiFe(H)(PMe3)2 (2), (2‐(iPr)2PC6H4)2HSiFe(H)(PMe3)2 (3) and (2‐(iPr)2PC6H4)2MeSiFe(H)(PMe3)2 (4)] as catalysts in the presence of (EtO)3SiH as dehydrating reagent was explored in the good to excellent yields. It was proved for the first time that Lewis acid could significantly promote this catalytic system under milder reaction conditions than other Lewis acid‐promoted system, such as shorter reaction time or lower reaction temperature. This is also the first example that dehydration of primary amides to nitriles was catalyzed by silyl hydrido iron complexes bearing [PSiP]‐pincer ligands with Lewis acid as additive. This catalytic system has good tolerance for many substituents. Among the four iron hydrides 1 is the best catalyst. The effects of substituents of the [PSiP]‐pincer ligands on the catalytic activity of the iron hydrides were discussed. A catalytic reaction mechanism was proposed. Complex 4 is a new iron complex and was fully characterized. The molecular structure of 4 was determined by single crystal X‐ray diffraction. [ABSTRACT FROM AUTHOR]

Thiol‐ and solvent‐coordinated cation exchange kinetics have been applied to engineer the composition and crystallinity of novel nanocrystals. The detailed thermodynamics and kinetics of the reactions were explored by NMR spectroscopy, time‐dependent photoluminescence (PL) characterizations and theoretical simulations. The fine structure of the colloidal semiconductor nanocrystals (CSNCs) was investigated by X‐ray absorption near‐edge structure (XANES) and extended X‐ray absorption fine structure (EXAFS). In this way, high‐quality p‐type Ag‐doped ZnS quantum dots (QDs) and Au@ZnS hetero‐nanocrystals with a cubic phase ZnS shell were synthesized successfully.The unprecedented dominant Ag+‐dopant‐induced fluorescence and p‐type conductivity in the zinc‐blende ZnS are reported. The right combination of thiol and solvent allows the resulting nanocrystal to be engineered by modulating the cation exchange kinetics. By applying this method, high‐quality p‐type Ag‐doped ZnS quantum dots (QDs) and Au@ZnS hetero‐nanocrystals with a cubic phase ZnS shell were synthesized successfully. [ABSTRACT FROM AUTHOR]

A discrete binuclear copper complex with nitrogen‐rich double rings has been synthesized by ether diffusion method, which was characterized by single crystal X‐ray diffraction. The crystal structure exhibits two connected rings as Arabic numeral "8" shape and stacks each other in the lattice leading to channels for ion sorption. Furthermore, this crystalline material is recoverable and displays high stability in water. The thermal stability has been confirmed by variable temperature powder X‐ray diffraction (VT‐PXRD). Flame atomic absorption spectrometry (FAAS) study has been carried out to confirm the ability of mercury(II) capture from aqueous solution, showing that the porous crystals have good adsorption capacity. The ion sorption kinetic process has been investigated, revealing a pseudo‐second‐order kinetics of mercury(II) adsorption. [ABSTRACT FROM AUTHOR]

Four silyl [P,Si]-chelate cobalt complexes ( 2- 5) have been synthesized through the chelate-assisted Si−H activation of bidentate preligand ortho-HSi(Me)2(PPh2)C6H4 ( 1) with CoMe(PMe3)4 and CoCl(PMe3)3. The silyl CoI complex, Co(PMe3)3(1-Si(Me)2-2-(PPh2)C6H4) ( 2), was synthesized by Si−H activation of 1 with CoMe(PMe3)4 or by combining complex 5 with MeLi and PMe3. Complex 2 was treated with CH3I or EtBr, generating the silyl CoII products CoI(PMe3)2(1-Si(Me)2-2-(PPh2)C6H4) ( 3) and CoBr(PMe3)2(1-Si(Me)2-2-(PPh2)C6H4) ( 4). The silyl CoIII hydride, CoHCl(PMe3)2(1-Si(Me)2-2-(PPh2)C6H4) ( 5), was obtained by the reaction of complex 1 with CoCl(PMe3)3. The catalytic performance of complex 5 was explored for Kumada coupling reactions, showing good to excellent catalytic efficiency with 2 mol % catalyst loading for the reactions of aryl chlorides or aryl bromides with Grignard reagents. It is noteworthy that the synthesis of 5 as a chelate complex is easier than that of previously reported [PSiP]-pincer cobalt hydride. With similar catalytic efficiency for Kumada reactions, the catalyst loading (2 %) of 5 was lower than that (5 %) of [PSiP]-pincer cobalt hydride. [ABSTRACT FROM AUTHOR]

Three ŋ4-(C=C-C=O) coordination cobalt(I) complexes 1-3 were synthesized by the reactions of cinnamaldehyde, p-fluorocinnamaldehyde and p-chlorocinnamaldehyde with CoMe(PMe3)4. Complex 4 as ŋ2-(C=C) coordination was prepared by the reaction of chalcone with Co(PMe3)4. The structures of complexes 1-4 were confirmedŋ4-Coordination; ŋ2-Coordination; Cinnamaldehyde; Cobalt by single-crystal X-ray diffraction. Although the reactions didn't undergo C-H bond activation and decarbonylation, the formation of complexes 1-4 deepens our understanding of the reactions between α,β-unsaturated aldehyde or ketone with low-valent central cobalt atom. [ABSTRACT FROM AUTHOR]

A 3D porous perchlorinated metal-organic framework (MOF), LIFM-26, featuring dual functionality, that is, functional polar groups and open metal sites, has been synthesized using perchlorinated linear dicarboxylate to link trigonal prismatic Fe3(μ3-O) units. LIFM-26 exhibits good thermal and chemical stability, and possesses high porosity with a BET surface area of 1513 m2 g−1, compared with isoreticular MOF-235 and Fe3O(F4BDC)3(H2O)3 (F4BDC=2,3,5,6-tetrafluorobenzene-1,4-dicarboxylate). Most strikingly, LIFM-26 features good gas sorption/separation performance at 298 K and 1 atm with IAST selectivity values reaching up to 36, 93, 23, 11, 46, and 202 for CO2/CH4, CO2/N2, C2H4/CH4, C2H6/CH4, C3H8/CH4, and R22/N2 (R22=CHClF2), respectively, showing potential for use in biogas/natural gas purification and CO2/R22 capture. [ABSTRACT FROM AUTHOR]

Two analogous M4L4-type tetrahedral cages (smaller: MOC-19; larger: MOC-22) were synthesized and investigated for their interactions with the anticancer drug 5-fluoracil (5-FU) by NMR spectroscopy, high-resolution electrospray-ionization mass spectrometry (HR-ESI-MS), and molecular simulation. The cage's size and window are of importance for the host-guest binding, and consequently the smaller MOC-19 with a more suitable size of cavity window was found to have much stronger hydrogen-bond interactions with 5-FU. The porous nanoparticles of MOC-19 exhibited outstanding behavior for the controlled release of 5-FU in a simulated human body with liquid phosphate-buffered saline solution. [ABSTRACT FROM AUTHOR]

Fluoroarylimine-stabilized iron(II) hydrides were used for the activation of CO2. The resulting iron(II) formate complex 6, which was obtained by formal CO2 insertion into the Fe-H bond, turned out to be unstable in solution. CO was suitable for the formation of stable analogues of complex 6. From the three-component reaction of CO, CO2, and iron hydride, a series of stable carbonyl formate iron(II) complexes 7- 9 were generated. Iron(II) formate complex 6 could also be obtained from the reaction of the iron(II) hydride complex with formic acid. On the basis of this result, the dehydrogenation of formic acid catalyzed by iron(II) hydrides was explored. The reaction was monitored by in situ 1H NMR spectroscopy, and a possible mechanism was proposed. In addition, iron(II) hydrides also reacted with CS2 to generate thiocarboxy iron(II) complexes 12, 13, 14, and 16. Unexpected complex 17 was produced from the three-component reaction of CS2, complex 4, and compound 15. The possible mechanism of the three-component reaction was also studied by operando IR spectroscopy. [ABSTRACT FROM AUTHOR]

To combine flexibility and modifiability towards a more controllable complexity of MOFs, a post-synthetic variable-spacer installation (PVSI) strategy is used to implement kinetic installation/ uninstallation of secondary ligands into/from a robust yet flexible proto-Zr-MOF. This PVSI process features precise positioning of spacers with different length, size, number, and functionality, enabling accurate fixation of successive breathing stages and fine-tuning of pore surface. It shows unprecedented synthetic tailorability to create complicated MOFs in a predictable way for property modification, for example, CO2 and R22 adsorption/separation, thermal/chemical stability, and extended breathing behavior. [ABSTRACT FROM AUTHOR]

To combine flexibility and modifiability towards a more controllable complexity of MOFs, a post-synthetic variable-spacer installation (PVSI) strategy is used to implement kinetic installation/ uninstallation of secondary ligands into/from a robust yet flexible proto-Zr-MOF. This PVSI process features precise positioning of spacers with different length, size, number, and functionality, enabling accurate fixation of successive breathing stages and fine-tuning of pore surface. It shows unprecedented synthetic tailorability to create complicated MOFs in a predictable way for property modification, for example, CO2 and R22 adsorption/separation, thermal/chemical stability, and extended breathing behavior. [ABSTRACT FROM AUTHOR]

Invited for the cover of this issue is the group of Marcel Mayor at the University of Basel with co‐workers Olaf Fuhr and Dieter Fenske from Karlsruhe Institute of Technology. The image depicts the studied all‐carbon polygon shaped macrocycles along with their intense circular dichroism spectra in the background. The bright light within the macrocycles displays its efficient conjugation. Read the full text of the article at 10.1002/chem.202201764. [ABSTRACT FROM AUTHOR]

Front Cover: Intense Molar Circular Dichroism in Fully Conjugated All-Carbon Macrocyclic 1,3-Butadiyne Linked pseudo-meta [2.2]Paracyclophanes (Chem. Eur. J. 53/2022) The angle and flexibility of the pseudo- I meta i substituents enabled high yielding macrocyclization reactions, and the studied trimeric, tetrameric, pentameric and hexameric structures further displayed astonishing through-space polymer-like conjugation lengths. Keywords: [2.2]paracyclophane; hydrocarbon; macrocycle; molar circular dichroism; -conjugation EN [2.2]paracyclophane hydrocarbon macrocycle molar circular dichroism -conjugation 1 1 1 09/27/22 20220922 NES 220922 B Unprecedented high molar circular b dichroism values for all-carbon macrocycles were revealed in 1,3-butadiyne bridged pseudo- I meta- i [2.2]paracyclophanes. [Extracted from the article]

Three diorganocobalt chlorides [CoClMe(PMe3)2-{(C5H6)- CH=O}] (4), [CoClMe(PMe3)2-{(C6H8)-CH=O}] (5), and [CoClMe(PMe3)2-{(C6H7Memeta)-CH=O}] (6) were synthesized through cyclometalation reactions with aldehyde as an anchoring group involving aliphatic vinylic C-Cl bond activation. Complexes 4-6 were characterized by IR and NMR spectroscopy. The crystal and molecular structures of complexes 4 and 5 were determined by single-crystal X-ray diffraction. Complexes 4-6 are stable in solution at room temperature, but they decompose at above 30°C affording C,C-couplings products with the formation of [Co(PMe3)3Cl]. The results of this work will be important for people to deepen the understanding of the C-Cl bond activation mechanism. [ABSTRACT FROM AUTHOR]

The silver salts of 1-adamantanethiol (AdSH) and furan-2-ylmethanethiol (FurCH2SH) were successfully applied as building blocks for ligand-protected Ag2S nanoclusters. The reaction of the silver thiolates [AgSAd]x and [AgSCH2Fur]x with S(SiMe3)2 and 1,5-bis(diphenylphosphino) pentane (dpppt) afforded three different clusters with 58, 94 and, 190 silver atoms. The intensely colored compounds [Ag58S13(SAd)32] (1), [Ag94S34(SAd)26(dpppt)6] (2), and [Ag190S58(SCH2Fur)74(dpppt)8] (3) were structurally characterized by single-crystal X-ray diffraction and exhibit different cluster core geometries and ligand shells. The diameters of the well-defined sphere-shaped nanoclusters range from 2.2 nm to 3.5 nm. [ABSTRACT FROM AUTHOR]

The silver salts of 1-adamantanethiol (AdSH) and furan-2-ylmethanethiol (FurCH2SH) were successfully applied as building blocks for ligand-protected Ag2S nanoclusters. The reaction of the silver thiolates [AgSAd]x and [AgSCH2Fur]x with S(SiMe3)2 and 1,5-bis(diphenylphosphino) pentane (dpppt) afforded three different clusters with 58, 94 and, 190 silver atoms. The intensely colored compounds [Ag58S13(SAd)32] (1), [Ag94S34(SAd)26(dpppt)6] (2), and [Ag190S58(SCH2Fur)74(dpppt)8] (3) were structurally characterized by single-crystal X-ray diffraction and exhibit different cluster core geometries and ligand shells. The diameters of the well-defined sphere-shaped nanoclusters range from 2.2 nm to 3.5 nm. [ABSTRACT FROM AUTHOR]

An M4L4 type metal-organic cage (MOC-19) has been synthesized from the one-pot reaction of tri(pyridinylmethylene)phenylbenzeneamine (TPBA) with hydrated Zn(ClO4)2 under mild conditions and characterized by single-crystal X-Ray diffraction. Iodine capture studies show that the porous crystals of MOC-19 exhibit a versatile behavior to accumulate iodine species not only in vapor (for I2) but also in solution (for I2 and I3−), and anion-exchange experiments indicate the capacity to extract IO3− anions from aqueous solution. Enrichment of iodine species from KI/I2 aqueous solution proceeds facilely, revealing a pseudo-second-order kinetics of I3− adsorption. Furthermore, the electrical conductivity of MOC-19 single crystals could be significantly altered by I2 inclusion. [ABSTRACT FROM AUTHOR]

Review: about 150 refs. [ABSTRACT FROM AUTHOR]

A series of luminescent polynuclear copper(I) phenyl thiolate clusters with functional groups in the organic ligand shell has been synthesized and characterized by single-crystal X-ray diffraction. Cluster compounds 1- 5 with Me2N groups bound to the phenyl thiolate are described and feature different nuclearities and core geometries. The heptanuclear compound 6, which contains both phenyl thiolate and Me3SiO functionalized phenyl thiolate ligands, is an unusual example of a mixed thiolate cluster and exhibits a core almost identical to that of 5. The optical properties of these compounds, which range from binuclear complexes with large Cu ···Cu distances to cluster molecules with seven copper atoms and relatively short Cu ···Cu distances, have been investigated. Compounds 1- 5 show strong absorption below 500 nm. The intense luminescence covers a wide range of the visible spectrum ( 1: green; 2 and 3: blue; 4 and 5: yellow). It seems likely that the optical transitions occur between orbitals of the thiol ligands and metal-centered orbitals; for the species with short Cu ···Cu distances ( 3- 5), these interactions cause a further redshift of the spectra. In addition, the influence of functional groups on optical absorption and emission is shown by the two Cu7 clusters 5 and 6, which differ solely in the electron-donating nature of their functional groups. [ABSTRACT FROM AUTHOR]

A series of phosphorus‐chalcogen chelated hydrido iron (II) complexes 1–7, (o‐(R'2P)‐p‐R‐C6H4Y)FeH (PMe3)3 (1: R = H, R' = Ph, Y = O; 2: R = Me, R' = Ph, Y = O; 3: R = H, R' = iPr, Y = O; 4: R = Me, R' = iPr, Y = O; 5: R = H, R' = Ph, Y = S; 6: R = Me, R' = Ph, Y = S; 7: R = H, R' = Ph, Y = Se), were synthesized. The catalytic performances of 1–7 for dehydration of amides to nitriles were explored by comparing three factors: (1) different chalcogen coordination atoms Y; (2) R' group of the phosphine moiety; (3) R substituent group at the phenyl ring. It is confirmed that 5 with S as coordination atom has the best catalytic activity and 7 with Se as coordination atom has the poorest catalytic activity among complexes 1, 5 and 7. Electron‐rich complex 4 is the best catalyst among the seven complexes and the dehydration reaction was completed by using 2 mol% catalyst loading at 60 °C with 24 hr in the presence of (EtO)3SiH in THF. Catalyst 4 has good tolerance to many functional groups. Among the seven iron complexes, new complexes 3 and 4 were obtained via the O‐H bond activation of the preligands o‐iPr2P(C6H4)OH and o‐iPr2P‐p‐Me‐(C6H4)OH by Fe(PMe3)4. Both 3 and 4 were characterized by spectroscopic methods and X‐ray diffraction analysis. The catalytic mechanism was experimentally studied and also proposed. [ABSTRACT FROM AUTHOR]

A catalytic system of regioselective synthesis of allyl sulfides via hydrothiolation of terminal arylallenes with arylthiols has been developed using nickel(0) complex Ni (PMe3)4 as a catalyst. In most cases the excellent to moderate yields were obtained under mild conditions. A catalytic mechanism was suggested and partially‐experimentally verified. To the best of our knowledge, this is the first example of regioselective addition of thiophenols to terminal arylallenes catalyzed by nickel(0) complex. It was noteworthy that this catalytic system was only applicable to thiophenol compounds with terminal arylallenes. [ABSTRACT FROM AUTHOR]

The cage's size and window are of importance for the host‐guest binding. 5‐Fluoracil can be preferentially captured by MOC‐19 in comparison to the larger MOC‐22 cage. The porous nanoparticle of MOC‐19 exhibits outstanding behaviors to control release of 5‐FU in simulated human body liquid PBS buffer. For more details, see the Communication by J. J. Jiang et al. on page 3542 ff. [ABSTRACT FROM AUTHOR]

A photograph is presented which explains the binding behavior between drug molecule 5-fluoracil and tetrahedral cages.