Beitr?ge zur Chemie des Schwefels. XIII

Ohne ZusammenfassungXII. Mitteilung: F. Fehér, W. Laue u. J. Kraemer: Z. Naturforsch. 7b, 574 (1952).     

The Tris(pentafluoroethyl)silanide Anion

Tris(pentafluoroethyl)silane, which is conveniently accessible by the treatment of Si(C₂F₅)₃X (X=Cl, Br) with Bu₃SnH, was successfully employed for hydrosilylation reactions. In the presence of a palladium catalyst, hydrosilylation of phenylacetylene with Si(C₂F₅)₃H affords the product of an α‐addition whereas the reaction of trimethylsilylacetylene with the silane leads to the β‐trans product. Tris(pentafluoroethyl)silane can be deprotonated by sterically demanding bases such as lithium diisopropylamide at low temperatures to give the corresponding silanide ion. The addition of crown ethers or cryptands to this highly reactive species enabled the isolation and characterization of salt‐like tris(pentafluoroethyl)silanide at room temperature.     

Nucleophilic Transfer Reactions of the [Si(C2F5)3]− Moiety

The tris(pentafluoroethyl)silanide anion is accessible by the deprotonation of Si(C₂F₅)₃H at low temperatures. Subsequent quenching of the resulting salt‐like compounds with suitable electrophiles, such as transition‐metal complexes or Group 14 element halides, leads to a plethora of novel tris(pentafluoroethyl)silane derivatives. This underlines the versatility of Li[Si(C₂F₅)₃] as a powerful nucleophilic transfer reagent.     

Visible Light Activation of Boronic Esters Enables Efficient Photoredox C(sp2)–C(sp3) Cross‐Couplings in Flow

We report herein a new method for the photoredox activation of boronic esters. Using these reagents, an efficient and high‐throughput continuous flow process was developed to perform a dual iridium‐ and nickel‐catalyzed C(sp²)–C(sp³) coupling by circumventing solubility issues associated with potassium trifluoroborate salts. Formation of an adduct with a pyridine‐derived Lewis base was found to be essential for the photoredox activation of the boronic esters. Based on these results we were able to develop a further simplified visible light mediated C(sp²)–C(sp³) coupling method using boronic esters and cyano heteroarenes under flow conditions.     

Dinuclear amine-thiophenolate complexes coligated by ferrocenemonocarboxylate and 1,1'-ferrocenedicarboxylate anions: preparation, characterization and structures of trinuclear [LMII 2(O2CC5H4FeCp)]+ and Pentanuclear [(LMII 2)2(O2CC5H4)2Fe]2+ complexes (M=Co, Ni, Zn)

A series of novel tri- and pentanuclear complexes composed of dinuclear LM(2) units (M=Co, Ni, Zn; L=24-membered macrocyclic hexaazadithiophenolate ligand) and ferrocenecarboxylate ([CpFeC(5)H(4)CO(2)](-)) or 1,1'-ferrocenedicarboxylate ([Fe(C(5)H(4)CO(2))(2)](2-)) groups is reported. The complexes [LM(II) (2)(O(2)CC(5)H(4)FeCp)](+) (M=Co (6), Ni (7), Zn (8)) and [(LM(II) (2))(2)(O(2)CC(5)H(4))(2)Fe](2+) (M=Co (9), Ni (10)) have been prepared by substitution reactions from labile [LM(II) (2)L'](+) precursors (L'=Cl, OAc) and the respective ferrocenecarboxylate anions in methanol. Mixed-valent [(LCo(II)Co(III))(2)(O(2)CC(5)H(4))(2)Fe](4+) (11) was prepared by oxidation of 9 with bromine. Complexes 7[BPh(4)], 8[BPh(4)], 9[BPh(4)](2), 10[BPh(4)](2), and 11[ClO(4)](4) have been characterized by X-ray crystallography; showing that the ferrocenyl carboxylates act as bidentate (7, 8) or bis-bidentate (9-11) bridging ligands towards one or two bioctahedral LM(2) subunits, respectively. The structures are retained in solution as indicated by NMR spectroscopic studies on the diamagnetic Zn(2)Fe complex 8[ClO(4)]. Electrochemical studies reveal significant anodic potential shifts for the oxidation potential of the ferrocenyl moieties upon complexation and the magnitude of the potential shift appears to correlate with the charge of the LM(2) subunits. This is qualitatively explained in terms of destabilizing electrostatic (Coulomb) interactions between the M(2+) ions of the LM(2) unit and the proximate ferrocenium fragment. An analysis of the temperature-dependent magnetic susceptibility data for 10[BPh(4)](2) shows the presence of weak ferromagnetic magnetic exchange interactions between the Ni(II) ions in the LNi(2) units. The exchange coupling across the ferrocenedicarboxylate bridge is negligible.     

Abnormal resting-state cortical coupling in chronic tinnitus

Background  

Subjective tinnitus is characterized by an auditory phantom perception in the absence of any physical sound source. Consequently, in a quiet environment, tinnitus patients differ from control participants because they constantly perceive a sound whereas controls do not. We hypothesized that this difference is expressed by differential activation of distributed cortical networks.     

Stiffness contribution of cellulose nanofibrils to composite materials

Nanocomposites, reinforced by different types of cellulose fibrils, have gained increased interest the last years due to the promising mechanical properties. There is a lack of knowledge about the mechanical properties of the cellulose fibrils, and their contribution to the often claimed potential of the impressive mechanical performance of the nanocomposites. This paper investigates the contribution from different types of cellulose nanofibril to the overall elastic properties of composites. A multiscale model is proposed, that allows back-calculation of the elastic properties of the fibril from the macroscopic elastic properties of the composites. The different types of fibrils used were nanofibrillated cellulose from wood, bacterial cellulose nano-whiskers and microcrystalline cellulose. Based on the overall properties of the composite with an unaged polylactide matrix, the effective longitudinal Young’s modulus of the fibrils was estimated to 65 GPa for the nanofibrillated cellulose, 61 GPa for the nano whiskers and only 38 GPa for the microcrystalline cellulose. The ranking and absolute values are in accordance with other studies on nanoscale morphology and stiffness estimates. Electron microscopy revealed that in the melt-processed cellulose nanofibril reinforced thermoplastics, the fibrils tended to agglomerate and form micrometer scale platelets, effectively forming a microcomposite and not a nanocomposite. This dispersion effect has to be addressed when developing models describing the structure–property relations for cellulose nanofibril composites.     

Resonant interband scattering of image-potential states

Image-potential states in front of a clean Cu (100) surface were investigated by time- and angle-resolved two-photon photo-emission (2PPE). We observe a previously unknown quasi-elastic relaxation channel, which efficiently couples states with different quantum numbers, n, and parallel momenta, k_∥. This process of resonant interband scattering (RIS) is independent of sample temperature and shows a close relationship to the pure dephasing of image-potential states. Received: 1 October 2001 / Revised version: 24 October 2001 / Published online: 23 November 2001