Heteroallen-komplexe des molybdänocens

Reactions of the extremely labile molybdenocene olefin complexe Mo(η⁵-C₅H₅)₂[(Z)-C₆H₅CH=CHC₆H₅] with heteroallenes X=C=Y (X=C=Y = CS₂, (p-tolyl)NCN(p-tolyl), (C₆H₅)₂CCO) gives the corresponding heteroallene complexes of molybdenocene Mo(η⁵-C₅H₅)₂(X=C=Y) in high yields. Spectroscopic data clearly indicate a dihapto-coordination of the heteroallenes via the C=X bond (X = O, S, N).     

Unexpected open-chain molecular structure of a titanocenyl-substituted dimethyl ether

Reaction of (η-C₅H₄CH₃)₂TiCl₂ with CH₃OCH₂MgCl yielded (η-C₅H₄-CH₃)₂Ti(Cl)CH₂OCH₃ (2a). Complex 2a crystallizes in space group P2₁/n with cell constants a 8.162(1), b 11.004(2), c 15.297(2) Å, β 96.40(1)°. In contrast to the three-membered metallacyclic zirconium compound of analogous composition (η-C₅H₅)₂Zr(Cl)CH₂OCH₃ (1), the titanocenyl-substituted ether 2a has an open-chain (η¹-O“-outside”) type structure.     

Zur entmischung der Lösungsmittel bei der chromatographischen trennung—v: Sorption von fliessmitteldämpfen an cellulose

The sorption of solvent vapours onto dried cellulose has been investigated. The time-dependence and the effect of the solvent-water ratio is discussed. The studies concerned the properties of methanol, ethanol, propanol and butanol.     

Elektronenstruktur,Spektren und Magnetismus von Chinon-π-Komplexen des Nickels

Zusammenfassung Die Elektronenstrukturen von Bis-durochinon-nickel(0) und der Komplexe vom Typ Olefin-Ni(0)-Chinon werden im Rahmen der LCAO-MO-Näherung diskutiert und zur Deutung der Absorptionsspektren herangezogen. Den im freien Durochmon auftretenden Übergängen lassen sich in den Komplexspektren jeweils nur wenig verschobene Banden zuordnen. Darüber hinaus wird eine intensive Charge-Transfer-Bande beobachtet, die einem Übergang vom höchsten besetzten Nickelzustand zum tiefsten unbesetzten Chinon-Orbital entspricht. Aus der Intensität der Bande, die im freien Chinon dem b _3g 2b ₂ g-Übergang zugeordnet wird, ergibt sich für das gelöste Bis-durochinon-nickel(0)-Molekül die Symmetrie D _2h . Während die Komplexe mit Durochinon in Übereinstimmung mit der Theorie diamagnetisch sind, weisen die analogen Verbindungen der Dimethylchinone magnetische Momente von 1,52 bzw. 2,75 B. M. auf, woraus auf eine Mitbeteiligung polarer Strukturen am Grundzustand dieser Komplexe geschlossen wird.

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The electronic structures of bis-duroquinone-nickel(0) and complexes of the type olefine-Ni(0)-quinone are discussed in the MO-LCAO approximation and used for an interpretation of the absorption spectra. The transitions of the free duroquinone can be correlated with transitions of the complexes at nearly the same wavelengths. In addition, an intense charge transfer band is observed which corresponds to a transition from the highest occupied nickel orbital to the lowest unoccupied quinone orbital. From the intensity of the band which corresponds to b _3g 2b_2g in the free quinone, the symmetry D _2h for the dissolved bis-duroquinone-nickel(0) molecule is deduced. Whereas the duroquinone complexes are diamagnetic in agreement with theory, analogous compounds of the diméthylquinones exhibit magnetic momenta of 1.52 and 2.75 B. M. suggesting the participation of polar structures in the ground state of these complexes.

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Résumé Les structures électroniques du bis-duroquinone-nickel(0) et des complexes du type oléfine-Ni(0)-quinone sont discutées dans le cadre del'approximationMO-LCAO et utilisées pour l'interprétation des spectres d'absorption. Aux transitions de la duroquinone libre peuvent être attribuées des bandes peu déplacées dans les spectres des complexes. En outre on observe une bande intense correspondant à une transition de la plus haute orbitale occupée du nickel à la plus basse orbitale libre de la quinone. L'intensité de la bande nommée b _3g 2b _2g dans la quinone libre indique la symétrie D _2h pour la molécule dissoute du bis-duroquinone-nickel(0). Tandis que les complexes de la duroquinone sont diamagnétiques en accord avec la théorie, des composés analogues des diméthylquinones présentent des moments magnétiques de 1,52 et de 2,75 B. M. d'où l'on infère la participation de structures polaires à l'état fondamental de ces complexes.

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6. Mitteilung über Komplexe vom Typ des Bis-durochinon-nickel(0). 5. Mitt. vgl. [11].     

TreeDock: a tool for protein docking based on minimizing van der Waals energies

Predicting protein-protein and protein-ligand docking remains one of the challenging topics of structural biology. The main problems are (i) to reliably estimate the binding free energies of docked states, (ii) to enumerate possible docking orientations at a high resolution, and (iii) to consider mobility of the docking surfaces and structural rearrangements upon interaction. Here we present a novel algorithm, TreeDock, that addresses the enumeration problem in a rigid-body docking search. By representing molecules as multidimensional binary search trees and by exploring a sufficient number of docking orientations such that two chosen atoms, one from each molecule, are always in contact, TreeDock is able to explore all clash-free orientations at very fine resolution in a reasonable amount of time. Due to the speed of the program, many contact pairs can be examined to search partial or complete surface areas. The deterministic systematic search of TreeDock is in contrast to most other docking programs that use stochastic searches such as Monte Carlo or simulated annealing methods. At this point, we have used the Lennard-Jones potential as the only scoring function and show that this can predict the correct docked conformation for a number of protein-protein and protein-ligand complexes. The program is most powerful if some information is known about the location of binding faces from NMR chemical-shift perturbation studies, orientation information from residual dipolar coupling, or mutational screening. The approach has the potential to include docking-site mobility by performing molecular dynamics or other randomization methods of the docking site and docking families to families of structures. The performance of the algorithm is demonstrated by docking three complexes of immunoglobulin superfamily domains, CD2 to CD58, the V(alpha) domain of a T-cell receptor to its V(beta) domain, and a T-cell receptor to a pMHC complex as well as a small molecule inhibitor to a phosphatase.     

Synthese und Reaktionen von Bicyclo[6.4.0]dodecan-3-carbonsäure-Derivaten

Synthesis and Reactions of the Bicyclo[6.4.0]dodecane-3-carboxylic Acid Derivatives The synthesis and some consecutive reactions of the compounds 5-8 , derivatives of bicyclo[6.4.0]dodecane-3-carboxylic acid ( 1 ), are described. The esters 7 and 8 can be obtained by Baeyer-Villiger oxidation of 2-hydroxy-8-methyltricyclo[7.3.1.0^2,7]tridecan-13-one ( 4 ) and subsequent hydrolysis of the lactone 5 . The structure and configuration of these compounds has been evaluated by spectroscopic techniques (mainly 2D-NMR methods). The formation of 7 via 1,2-H shift and subsequent isomerization to 8 has been studied. The esters 11 and 13 are formed stereospecifically from 7 and 8 .     

Purification and analysis of partially alkylated cyclodextrins by liquid and gas chromatography

Complex mixtures of partially alkylated cyclodextrins can be analyzed by both HPLC and high temperature capillary GC. Because of the limited efficiency of LC, suitable analytical and preparative separations can be achieved only with systems of carefully optimized selectivity. Using LC it has been possible to isolate and purify single cyclodextrin species from very complex mixtures of components which contain unreacted hydroxyl groups in addition to the alkoxy groups. Analysis of the reaction mixtures and of fractions taken from LC separations can be performed with advantage by high resolution capillary GC at high temperatures between 300 and 400 °C. The thermal stability of partially alkylated cyclodextrins in high temperature GC is considerably increased by trimethylsilylation of the free hydroxyl groups. Fast atom bombardment mass spectrometry and proton NMR were used to identify species isolated from the preparative LC separations.     

Zur Lokalisierung funktioneller Gruppen mit Hilfe der Massenspektrometrie. XVII—Massenspektren von 3,6,20β-Trihydroxy-pregnanen

Mass spectra of 3,6,20β-trihydroxypregnanes differ greatly, depending upon the nature of the A/B ring fusion and the positions of the hydroxy groups. Of all the isomers only 3α,6β,20β-trihydroxy-5β-pregnane produces an intense, structurally significant, ion at m/e 263. For 3β,6α,20β-trihydroxy-5α-pregnane an ion of m/e 141 is typical.     

Chemie der Pleuromutiline,IX. Konfigurationsumkehr der Methylgruppe am Kohlenstoff 6 im tricyclischen Gerüst des Diterpens Pleuromutilin

The contact of pleuromutilin derivatives with the protein moiety of cytochrome P-450 as well as its orientation towards the heme iron is mainly dependent on the steric environment of the hydrindanone-part of the tricyclus. The apparent affinity between substrate and enzyme, which is correlated with the rate of metabolism can be reduced by inversion of configuration at carbon 6. This inversion is achieved by equilibrating the diastereomeric ketones12 and13 followed by a selective reduction of the keto group at position 7. The 6-methylgroup of14 was assigned α-configuration on the basis of spectroscopic data in comparison to those of the naturally configurated compound14a.