Fluorescent non-linear chiral polymer chemosensor bonded alternatively with 1,4-diethynyl-2,5-dioctyloxybenzene and (R,R)-salen for Zn2+recognition

Stereoregular non-linear chiral main chain polymers 1a–b bonded alternatively with (R,R)-salen and 1,4-diethynyl-2,5-dioctyloxybenzene moieties have been synthesized using palladium catalyzed C–C cross-coupling and Schiff base formation reactions as the key steps. These polymers are soluble in common organic solvents, and act as an effective chemosensor for the detection of Zn²⁺ with respect to other metal ions with enhanced fluorescence. The CD spectra observed for the polymers 1a–b could be attributed to the helical secondary structure with a low degree of inter-strand interactions. This reduced inter-strand interaction has been ascertained from the titration of pyridine to the Zn(II)-polymer 1b complex, which results in minor changes in the fluorescence emission.     

ORGANOSTANNOXANE MOTIFS IN CAGES AND SUPRAMOLECULAR ARCHITECTURES

The reactions of n-butyl stannonic acid with(PhO) ₂ P(O)H leads to the formation of a hexameric tin cage [{(n-BuSn) ₃ (PhO) ₃ O} ₂ {HPO ₃ } ₄ ].This reaction involves an in situ P─O bond cleavage and the generation of a [HPO ₃ ] ^2? ion. A direct reaction of six equivalents of n-BuSnO(OH) acid with six equivalents of C ₆ H ₅ OH and four equivalents of H ₃ PO ₃ also leads to the formation of same cage structure. A tetranuclear organooxotin cage[(PhCH ₂ ) ₂ Sn ₂ O(O ₂ P(OH)-t-Bu) ₄ ] ₂ has been assembled by debenzylation involving the reaction of (PhCH ₂ ) ₂ SnCl ₂ ,(PhCH ₂ ) ₂ SnO·H ₂ O or (PhCH ₂ ) ₃ SnCl with two equivalents of t-BuP(O)OH ₂ . A half-cage intermediate [(PhCH ₂ ) ₂ Sn ₂ O(O ₂ P(OH)-t-Bu) ₄ ] has been detected. New organotin cations of the type [n-Bu ₂ Sn(H ₂ O) ₄ ] ²⁺[2,5-Me ₂ -C ₆ H ₃ SO ₃ ]^? ₂ and {[n-Bu ₂ Sn(H ₂ O) ₃ LSn(H ₂ O) ₃ (n-Bu) ₂ ] ²⁺[1,5-(SO ₃ ) ₂ -C ₁₀ H ₆ ] ^2?} have been obtained in the reactions of n-Bu ₂ SnO or (n-Bu ₃ Sn) ₃ O with 2,5-dimethyl sulfonic acid and 1,5-naphthalene disulfonic acid respectively. These organotin cations form interesting supramolecular structures in the solid state as a result of O─H─···O hydrogen bonding.     

Can Low‐Valent Germanium Chemistry Be Practiced Under Ambient Conditions? A Tale of a Water‐Stable Yet Reactive Germylene Monochloride Complex

A germylene monochloride complex ((DPM)GeCl, 1 ) that is water stable was isolated for the first time. Interestingly, it reacts with cesium fluoride under ambient conditions (non‐inert atmosphere and water‐containing solvent) to afford water stable germylene monofluoride complex ((DPM)GeF, 2 ). Due to the usage of DPM (dipyrrinate) ligand, germylene monohalides 1 and 2 show fluorescence in the visible region at 555 and 538 nm, respectively. Compounds 1 and 2 are the first fluorescent germylene complexes and were characterized by multinuclear NMR spectroscopy. The structure of compound 1 was also proved by single crystal X‐ray diffraction studies.     

Si-O and P-O motifs in inorganic rings and clusters

This article presents a brief overview of different kinds of silanols and the important reactions of N-bonded silanetriols. The synthesis and characterization of silanediols containing Si-N and Si-C bonds, (2,4,6-Me₃C₆H₂)N(SiMe₃)Si(Me)(OH)₂ (1e) is described. 1e shows a polymeric crinkled tape type of structure due to extensive intermolecular hydrogen bonding. We also describe the formation of a neutral copper(II) complex derived from the reaction of CuCl₂ with (O)P(3,5-Me₂Pz)₃ where the ligand undergoes a facile P-N bond cleavage and functions as an N₂O type of tridentate ligand.     

Copper(II)-catalyzed conversion of bisaryloxime ethers to 2-arylbenzoxazoles via C-H functionalization/C-N/C-O bonds formation

A copper(II)-catalyzed conversion of bisaryloxime ethers to 2-arylbenzoxazoles has been developed. The reaction involves a cascade C-H functionalization and C-N/C-O bond formation under oxygen atmosphere.     

A reactivity change of a strontium monohydroxide by umpolung to an acid

Controlled hydrolysis of strontium amide LSrN(SiMe 3) 2(thf) (L = CH(CMe2,6- i-Pr 2C 6H 3N) 2) ( 1) gave an unprecedented example of a hydrocarbon-soluble strontium hydroxide, [LSr(thf)(mu-OH) 2Sr(thf) 2L] ( 2). In compound 2, the tetrahydrofuran (THF) molecules can easily replaced by benzophenone and triphenylphosphine oxide to yield [LSr(mu-OH)(OCPh 2)] 2 ( 3) and [LSr(mu-OH)(OPPh 3)] 2 ( 4) compounds. Among the two strontium atoms of 2, one is coordinated to a single THF molecule, while the other is coordinated to two THF molecules. Interestingly, strontium hydroxide complex 2 behaves as an acid in its reaction with Zr(NMe 2) 4 and results in a heterobimetallic oxide, [LSr(mu-O)Zr(NMe 2) 3] 2 ( 5). Compound 5 is dimeric in the solid state and contains a Sr 2Zr 2O 2 core.     

First example of a Sn-C bond cleaved product in the reaction of Ph3SnOSnPh3 with carboxylic acids. 3D-supramolecular network formation in the X-ray crystal structure of [Ph2Sn(OH)OC(O)(Rf)]2, Rf = 2,4,6-(CF3)3C6H2

A 1:2 reaction of Ph3SnOSnPh3 1 with RfCOOH 2 leads to the formation of [Ph2Sn(OH)OC(O)(Rf)]2 3, by means of a facile Sn-C bond cleavage process.     

A lipophilic hexaporphyrin assembly supported on a stannoxane core

Lipophilic hexaporphyrin free-base and copper-metalated assemblies supported on a Sn6O6 core have been synthesized and characterized. The nuclease activity of the copper derivative has been studied.     

Copper(II)‐Catalyzed Nitroaldol (Henry) Reactions: Recent Developments

Self‐assembled copper(II) complexes are described as effective catalysts for nitroaldol (Henry) reactions on water. The protocol involves a heterogeneous process and the catalysts can be recovered and recycled without loss of activity. Further, C2‐symmetric N,N′‐substituted chiral copper(II) salan complexes are found to be more effective catalysts than chiral copper(II) salen complexes for reactions in homogeneous catalysis, with high enantioselectivities. The reactions involve bifunctional catalysis, bearing the properties of a Brønsted base, as well as a Lewis acid, to effect the reaction in the absence of external additives.