N(SCl)2 ⊕[MoCl5(NSCl)]⊖, ein Chlorthionitrenokomplex von Molybdän(VI)

N(SCl)₂^⊕ [MoCl₅(NSCl)]^?, a Chlorothionitrene Complex of Molybdenum (VI) . The title compound is formed together with MoCl₃(N₃S₂) by the reaction of MoCl₄ or MoCl₅ with (NSCl)₃ in CH₂Cl₂. The black, crystalline compound was characterized by its i.r. spectrum and an X-ray crystal structure determination. N(SCl)₂^⊕[MoCl₅(NSCl)]^? crystallizes in the monoclinic space group P2₁/n with four formula units per unit cell. The lattice constants are a = 716.3, b = 1627.4, c = 1178.9 pm and β = 100.90°. The [MoCl₅(NSCl)]^? ion posseses an almost linear Mo = N = S grouping with bond lengths that can be interpreted as double bonds. Crystal data for AsPh₄[MoCl₅(NSCl)] are reported.     

Fluordiazadiphosphetidine, 11. Mitt.: Eine neue Methode zur Herstellung der doppelt zwitterionischen Verbindung (CH3N)6P4F8

A new synthetic route for the preparation of the betain-like compound (CH₃N)₆P₄F₈ from (CH₃NPF₃)₂,N-methyl-hexamethyldisilazane andN,N-dimethyl-urea has been found. The steps of this multi-stage reaction could be rationalized to a far extent.

10. Mitteilung:Kubjacek M., Utvary K., Mh. Chem.112, 305 (1981).     

The Synthesis of 4b, 5, 12, 12a-Tetrahydro-5, 12-ethano-13H-indeno[2,3-b]anthracenes, 4b, 5, 10, 10a - tetrahydro-5,10-ethano-11H-indeno[2,3-b]naphtalenes and 1,2,3,4,4a, 9a-Hexahydro-1,4-(peri-naphthaleno)-fluorenes

The synthesis of endo- and exo-13-oxo-4b, 5, 12, 12a-tetrahydro-5, 12-ethanoindeno[2,3-b]anthracene ( 23 ; Schemes 1 and 2), exo- and endo-11-oxo-4b, 5, 10, 10a-tetrahydro-5, 10-ethano-indeno[2,3-b]naphthalene ( 31 ; Scheme 3), 1,2,3,4,4a,9a-hexahydro?1,4-(peri-naphthaleno)-fluoren-9-one (36; Scheme 4), and the corresponding hydrocarbons of the stereoisomeric ketone pairs 23 and 36 , is described.     

Synthese,IR-Spektrum und Kristallstruktur von N,N'-Bis(trimethylsilyl)benzamidinium-tetrachloroferrat(III)

Synthesis, IR Spectrum, and Crystal Structure of N,N'-Bis(trimethylsilyl)benzamidinium Tetrachloroferrate(III) The title compound [C₆H₅? C(NHSiMe₃)₂][FeCl₄] is obtained by the reaction of FeCl₃ with N,N,N'-tris(trimethylsilyl)benzamidine in the presence of tetrahydrofurane, forming yellow, moisture sensitive crystals. The compound is characterized by its IR spectrum as well as by an X-ray structure determination. Space group P2₁/n, Z = 8, 5974 independent observed reflexions, R = 0.066. The lattice dimensions are at ?70°C: a = 2110.7, b = 1109.5, c = 2120.4 pm; β = 111.17º. The compound forms ion pairs, in which the H atoms of the amidinium cation are coordinated with one chlorine ligand of the FeCl₄^? ion in a chelating manner.     

Enantioselektive Reaktionen an porphinoiden Nickelkomplexen

Enantioselective Reactions on Porphine Type Nickel Complexes The thermodynamically controlled addition of alcohols to (+)-(1R)-[1-methyl-8H-HDP]nickelperchlorate ( 1 ; e.e. 92%) yields exclusively the corresponding cis-1,11-disubstituted porphinoids. Chemical transformation of functional groups in the alkoxy side-chain of the chiral addition product followed by acid catalyzed elimination yields the derived alcohols and 1 . By this procedure, the following enantioselective transformations were studied: methylation of meso-2,3-butandiol ( 5 ) to (+)-(2R,3S)-3-methoxy-2-butanol ( 8a ; e.e. 87%), diimide reduction of 2-ethylallyl alcohol ( 9 ) to (+)-(2R)-2-methyl-1-butanol ( 12a ; e.e. 15%), and hydride reduction of 4-hydroxy-2-butanone ( 13 ) to (+)-(3S)-1,3-butandiol ( 16a ; e.e. 20%). Addition of 2,2-dimethyl-1,3-propandiol ( 17 ) to 4 , followed by esterification of the free hydroxy group with trifluoromethanesulfonic anhydride and solvolysis of the sulfonate 19 yielded a bridged complex with unrearranged alkyl chain for which structure 20 is proposed.     

Monocyclopentadienylhydride derivatives of ruthenium: stereoselective proton transfer and proton-hydride exchange in an extremely short dihydrogen bond

Diastereomerically pure complexes of formula CpRuCl(PP) and CpRuH(PP) with chiral ferrocenyl diphosphines were prepared and the selectivity of proton-transfer processes over the monohydride compounds with different acids was studied. With 1 equiv of HBF(4) the cis-dihydrogen and trans-dihydride complexes were formed while with 3 equiv of CF(3)CO(2)H the trans-dihydride derivative was the only product. However, the use of 1 equiv of CF(3)CO(2)H led to a dihydrogen bonded complex with an extremely short RuH...HO(2)CF(3) interaction that exhibits proton-hydride exchange. Using the labeled acid CF(3)CO(2)D, a stereoselective transference of the deuteron was demonstrated that implies the previous epimerization of the monohydride and the subsequent attack of the acid in the position previously occupied by the hydride.     

Tuning cell adhesion on gradient poly(2-hydroxyethyl methacrylate)-grafted surfaces

A simple yet versatile method was developed to prepare a low-density polymerization initiator gradient, which was combined with surface-initiated atom transfer radical polymerization (ATRP) to produce a well-defined poly(2-hydroxyethyl methacrylate) (HEMA) gradient substrate. A smooth variation in film thickness was measured across the gradient, ranging from 20 A to over 80 A, but we observed a nonmonotonic variation in water contact angle. Fits of X-ray reflectivity profiles suggested that at the low graft density end, the polymer chain structure was in a "mushroom" regime, while the polymer chains at high graft density were in a "brush" regime. It was found that the "mushroom" region of the gradient could be made adhesive to cells by adsorbing adhesion proteins, and cell adhesion could be tuned by controlling the density of the polymer grafts. Fibroblasts were seeded on gradients precoated with fibronectin to test cellular responses to this novel substrate, but it was found that cell adhesion did not follow the expected trend; instead, saturated cell adhesion and spreading was found at the low grafting density region.     

Biocatalytic asymmetric hydrogen transfer employing Rhodococcus ruber DSM 44541

Nonracemic sec-alcohols of opposite absolute configuration were obtained either by asymmetric reduction of the corresponding ketone using 2-propanol as hydrogen donor or by enantioselective oxidation through kinetic resolution of the rac-alcohol using acetone as hydrogen acceptor employing whole lyophilized cells of Rhodococcus ruber DSM 44541. The microbial oxidation/reduction system exhibits not only excellent stereo- and enantioselectivity but also a broad substrate spectrum. Due to the exceptional tolerance of the biocatalyst toward elevated concentrations of organic materials (solvents, substrates and cosubstrates), the process is highly efficient. The simple preparation of the biocatalyst and its ease of handling turns this system into a versatile tool for organic synthesis.     

Nicolaus Cusanus und implizite Funktionen

Mathematische Semesterberichte - Nicolaus Cusanus’ Beiträge zur Mathematik des 15. Jahrhunderts betreffen hauptsächlich Kreisquadraturen. Wir besprechen seinen...