Enhancing the Water Stability of Al‐MIL‐101‐NH2 via Postsynthetic Modification

The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH₂ by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N₂ and H₂O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m² g^?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with ¹H‐²⁷Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking.     

Consecutive reactions of diethoxydimethylsilane and triethoxymethylsilane with methoxide ions in methanol solution

The consecutive reactions of (CH₃)₂Si(OC₂H₅)₂ and CH₃Si(OC₂H₅)₃ with methoxide ions were investigated in methanol solutions. The reverse transesterification reactions with ethoxide ions could be neglected in both cases since the concentration of ethoxide in methanol solution was assumed to be low due to the fast equilibrium reaction C₂H₅O^? + CH₃OH ? C₂H₅OH + CH₃O^?. The progress of the reactions was followed by monitoring the formation of ethanol with a Fourier-transform infrared spectrometer. All rate constants were determined at 295 K. The reactions between the dialkoxydimethylsilanes and methoxide ions were assumed to consist of two consecutive steps that can be represented by the net reaction; (CH₃)₂Si(OC₂H₅)₂ + 2CH₃O^? → (CH₃)₂Si(OCH₃)₂ + 2C₂H₅O^?. The two consecutive rate constants were established as 1.93 ± 0.12M^?1s^?1 and 1.00 ± 0.12M^?1s^?1, respectively. The consecutive rate constants for the reactions between the trialkoxymethylsilanes and methoxide ions can be written according to the total reaction; CH₃Si(OC₂H₅)₃ + 3CH₃O^? → CH₃Si(OCH₃)₃ + 3C₂H₅O^?. The three rate constants corresponding to each consecutive step were established as 1.12 ± 0.09 M^?1s^?1, 0.82 ± 0.10 M^?1s^?1, and 0.51 ± 0.06 M^?1s^?1, respectively. © 1995 John Wiley & Sons, Inc.     

Diels-Alder-Reaktionen von Vinylindolen mit Arin und 1,4-Benzochinonen: Neue potentielle DNA-Interkalatoren

Summary Diels-Alder reactions of 2- and 3-vinylindoles with aryne, 1,4-benzo- and 1,4-naphtho-quinone lead to new six-ring annellated carbazoles. Molecular modeling studies predict that the compounds with coplanar framework are able to intercalate with the B-DNA.

     

Multicenter ligand transformations of thioureas on ruthenium clusters

The reaction of trirutheniumdodecacarbonyl with various thioureas was found to give, depending upon the substituents and the reaction conditions, a large variety of tri-, tetra-, penta-, and hexanuclear ruthenium clusters. The ligand systems observed in the products are derived from the thioureas employed; the fragmentation of the thiourea molecules involve N-H, C-S, C-H, and C-N activation processes.     

Chain “stationary” insertion mechanism and production of isotactic polypropylene with C 1 symmetric catalyst systems

In this contribution, the stereochemistry of propylene insertion/propagation reactions with a variety of C ₁ symmetric metallocene catalysts, containing bridged cyclopentadienyl-fluorenyl ligand for the preparation of highly stereoregular polypropylene is presented. The impact of the distal substitutent’s size and composition and changes that the catalytic sites undergo upon such substitution is elaborated. A comprehensive mechanism is proposed to explain the resulting catalytic changes that bring about the irreversible C _s/C ₁ site transformation and tactic behavior inversion. Furthermore the cyclopentadienyl’s combined distal/proximal and fluorenyl’s frontal substituent effects on molecular weight, regio-, and stereoregularity of the final polymers are discussed. Finally, stereoselectivities of C ₂ and C ₁ symmetric catalyst systems are compared. It is shown that current high performance C ₁ symmetric catalyst systems with central site chirality can be isotactic selective as well or even better in certain aspects than the C ₂ symmetric bridged bisindenyl-based metallocene catalysts. The text was submitted by the authors in English.