Synthesis and Reactivity of the First Isolated Hydrogen‐Bridged Silanol–Silanolate Anions

We report on the first examples of isolated silanol–silanolate anions, obtained by utilizing weakly coordinating phosphazenium counterions. The silanolate anions were synthesized from the recently published phosphazenium hydroxide hydrate salt with siloxanes. The silanol–silanolate anions are postulated intermediates in the hydroxide‐mediated polymerization of aryl and alkyl siloxanes. The silanolate anions are strong nucleophiles because of the weakly coordinating character of the phosphazenium cation, which is perceptible in their activity in polysiloxane depolymerization.     

Ab initio predictions of zeolite structures and Si NMR chemical shifts

A recent shell-model potential parameterized on ab initio data is used for predicting the all-silica structures of zeolites MFI, MEI, MTW, TON, FAU and of α-quartz. Cluster models are defined around each site and the ²⁹Si NMR shielding constants are calculated by ab initio techniques (GIAO-HF). Good agreement with observed ²⁹Si NMR chemical shifts is found. Comparison is made with shifts calculated for observed structures. The structures predicted by the ab initio shell-model potential prove as accurate as the observed ones when judged on the quality of the calculated ²⁹Si NMR spectra.     

1.2-Bis(pentamethylcyclopentadienyl)tetrachlorodisilane and its reduction to decamethylsilicocene

Reaction of pentamethylcyclopentadienyl(pentachloro)disilane (2), prepared from hexachlorodisilane and potassium pentamethylcyclopentadienide (Cp^*K), with a further equivalent of Cp^*K leads selectively to the title compound Cp^* ₂ Si ₂ Cl ₄ (3) which was characterized by NMR and X-ray structural data. Dehalogenation of 3 with four equivalents of sodium naphthalenide offers an alternative route for the synthesis of decamethylsilicocene (1). Dedicated to Professor Mitsuo Kira on the occasion of being honoured with the Wacker Silicon Award 2005.     

Concerning the Thermal Diastereomerization of the Green Fluorescent Protein Chromophore

Summary. Two model compounds for the green fluorescent protein chromophore were prepared. One of them incorporates the natural 4-hydroxybenzylidene group of the natural tyrosin derived chromophore, the other one bears a methyl group instead of the hydroxy group. Whereas the photochemically prepared (E)-diastereomer of the first compound very effectively reverted thermally (room temperature) to the thermodynamically stable (Z)-diastereomer, the (E)-diastereomer of the second derivative proved to be stable even at elevated temperatures for more than a day. This finding can be rationalized by constructing the appropriate resonance structures showing that only in the first case an effective delocalization enables partial single bond character of the benzylidene double bond. From the standpoint of chemical etiology, only Nature’s choice of the tyrosin derived chromophore of the green fluorescent protein provides an efficient radiationless thermal relaxation channel for the unwanted photo-diastereomerization product formed after excitation besides the dominating fluorescence channel of its chromophore.     

Lanthanoid-nickel-phosphides with ThCr2Si2-type structure

The new compounds YNi₂P₂ and LnNi₂P₂ (Ln = La, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm) were prépared by sintering the elemental components in silica tubes. Well-developed crystals were obtained using tin as a flux. They crystallize with the ThCr₂Si₂ (CeGa₂Al₂)-type structure which was refined from single-crystal X-ray data for EuNi₂P₂ to a conventional R value of 0.049 for 118 unique structure factors. While the P atoms in formally isotypic EuCo₂P₂ are isolated from each other, they form pairs in EuNi₂P₂. This results in a different $\text{c}\text{a}$ ratio and an entirely different bonding situation. A comparison of cell volumes shows that Eu in EuNi₂P₂ has an intermediate valence.     

Solid-Phase Synthesis of a Sialyl-Tn-Glycoundecapeptide of the MUC1 Repeating Unit

The synthesis of glycopeptides carrying tumour-associated antigens is of interest for cancer diagnosis and treatment. Here, a very efficient route lo disaccharide threonine building block 8 is presented which allows the introduction of the sialyl-Tn antigen into a peptide. The syntheses of the undecapeptide and the sialyl-Tn-containing glycoundecapeptide, which are a part of the repeating unit of MUC1, were performed by solid-phase synthesis with an allylic anchor cleavable under neutral conditions. After detachment from the resin, the peptide and the glycopeptide arc completely deprotected giving the target compounds 13 and 15 , respectively.     

Advanced approaches for the characterization of a de novo designed antiparallel coiled coil peptide

We report here an advanced approach for the characterization of the folding pattern of a de novo designed antiparallel coiled coil peptide by high-resolution methods. Incorporation of two fluorescence labels at the C- and N-terminus of the peptide chain as well as modification of two hydrophobic core positions by Phe/[15N,13C]Leu enable the study of the folding characteristics and of distinct amino acid side chain interactions by fluorescence resonance energy transfer (FRET) and NMR spectroscopy. Results of both experiments reveal the antiparallel alignment of the helices and thus prove the design concept. This finding is also supported by molecular dynamics simulations. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) in combination with NMR experiments was used for verification of the oligomerization equilibria of the coiled coil peptide.     

Routes to unique palladium A-frame complexes with a bridging fluoro-ligand

Treatment of a toluene solution of [PdMe(2)(Cy(2)PCH(2)PCy(2))](1) with pentafluoropyridine in the presence of traces of water affords the generation of the A-frame complexes [(PdMe)(2){mu-kappa(2)(P,P)Cy(2)PCH(2)PCy(2)}(2)(mu-F)][SiMeF(4)]() and [(PdMe)(2){mu-kappa(2)(P,P)Cy(2)PCH(2)PCy(2)}(2)(mu-F)][OC(5)NF(4)](2b). If the reaction is performed in an NMR tube equipped with a PFA inliner, complex 2b is produced, only. Treatment of 1 with pentafluoropyridine in the presence of an excess water yields the pyridyloxy complex [PdMe(OC(5)NF(4))(Cy(2)PCH(2)PCy(2))](3). Compound [(PdMe)(2){mu-kappa(2)(P,P)Cy(2)PCH(2)PCy(2)}(2)(mu-F)][FHF](2c) bearing a bifluoride anion instead of SiMeF(4)(-) or OC(5)NF(4)(-) can be generated by reaction of 1 with substoichiometric amounts of Et(3)N.3HF. The analogous complex [(PdMe)(2){mu-kappa(2)(P,P)Ph(2)PCH(2)PPh(2)}(2)(mu-F)][FHF] (5c) has been synthesized by addition of Ph(2)PCH(2)PPh(2) to a solution of [PdMe(2)(Me(2)NCH(2)CH(2)NMe(2))](4) in THF and subsequent treatment of the reaction mixture with Et(3)N.3HF. The structure of the A-frame complex 5c has been determined by X-ray crystallography.     

A simple adsorption model for ionic surfactants

In the past, few theoretical attempts have been made to describe quantitatively the adsorption of ionic surfactants at liquid interfaces. Well-known adsorption isotherms due to Frumkin or Hill–de Boer cannot respond to the specific electrostatic and geometric properties of the surfactant molecules. Our approach is based on a combination of the Gouy–Chapman theory with a modified Frumkin isotherm. The modification implies that the system is free to choose an optimal head group area and an optimal arrangement of the surfactant molecules in the interface as a function of bulk concentration. Interaction energies between neighbouring adsorbed surfactant molecules and between surfactant and water molecules are taken into consideration. The minimum of the Gibbs free energy of the system is equivalent to a minimal interfacial tension. Thus, the thermodynamically stable isotherm can be obtained as the lower envelope of the family of σ versus ln c isotherms resulting from different choices of the model parameters, including the area per molecule. According to the Gibbs equation, the Γ versus ln c adsorption isotherm is obtained as the derivative of this envelope. By variation of the model parameters, the envelope of the calculated adsorption isotherms can be fitted to experimental data of the interfacial tension versus bulk concentration. A computer program is used to calculate the σ versus c and the Γ versus ln c curves as well as to fit the parameters. Received: 28 October 1999/Accepted: 8 February 2000     

Stabilisation of [Fe2(CO)9] and [Ru2(CO)9] bu substitution with bridging diphosphorus ligands

Reaction of [Fe₂(CO)₉] with a half molar amount of R₂PYPR₂ (Y = CH₂, R = Ph, Me, OMe or OPrⁱ; Y = N(Et), R = OPh, OMe or OCH₂; Y = N(Me), R = OPrⁱ or OEt) leads to the ready formation of a product which on irradiation with ultraviolet light rapidly decarbonylates to the heptacarbonyl derivative [Fe₂(μ-CO)(CO)₆{μ-R₂PYPR₂}]. Treatment of the latter with a slight excess of the appropriate ligand results, under photochemical conditions, in the formation of the dinuclear pentacarbonyl complex [Fe₂(μ-CO)(C))₄{μ-R₂PYPR₂}₂] but under thermal conditions in the formation of the mononuclear species [Fe(CO)₃{R₂PYPR₂}]. Reaction of [Ru₃(CO)₁₂] with an equimolar amount of (RO)₂PN(R′)P(OR)₂ (R′ = Me, R = Prⁱ or Et; R′ = Et, R = Ph or Me) under either thermal or photochemical conditions produces [Ru₃(CO)₁₀{μ-(RO)₂PN(OR)₂}] which reacts further with excess (RO)₂PN(R′)P(OR)₂ on irradiation with ultraviolet light to afford the dinuclear compound [Ru₂(μ-CO)(CO₄{μ-(RO)₂PN(R′)P(OR)₂}₂]. The molecular structure of [Ru₂(μ-CO)(CO)₄{μ-(MeO)₂PN(Et)P(OMe)₂}₂], which has been determined by X-ray crystallography, is described.