The reaction of the alkyl complexes Cp*2LnCH(SiMe 3)2 (Ln = Y 1-Y, Ce 1-Ce, La 1-La; Cp* = η5-C5Me5) and Me2Si(η 5-C5Me4)2LnCH(SiMe3) 2 (Ln = Ce 5-Ce) with 1-methylalk-2-ynes CH3C≡CR (R = Me 3a, Et 3b, nPr 3c, tBu 3d, SiMe3 3e, Ph 3f, C6H4Me-2 3g, C6H3Me 2-2,6 3h, C6H3iPr2-2,6 3i, C6F5 3j) affords the corresponding η3-propargyl/allenyl complexes Cp*2LnCH 2CCR (4a-j-Ln) and Me2Si(η5-C 5Me4)2CeCH2CCR (6a-j-Ce) via propargylic metalation. The hydride complexes [Cp*2Ln(μ-H)] 2 (Ln = Y 2-Y, Ce 2-Ce, La 2-La) react rapidly with 3 to produce mixtures of insertion and propargylic metalation products, and the relative rate of these processes depends on the metal and alkyne substituent. Selected η3-propargy/allenyl complexes Cp*2YCH 2CCR (R = Me 4a-Y, Ph 4f-Y), Cp*2CeCH2CCR (R = Me 4a-Ce, Ph 4f-Ce), Cp*2CeCH(Me)CCEt (9b-Ce), Cp*2LaCH2CCR (R = Ph 4f-La, C6H 3Me2-2,6 4h-La) are obtained on a preparative scale and characterized by NMR spectroscopy, IR spectroscopy, and cryoscopy. Compounds 4f-Y and 4f-La are also characterized by single-crystal X-ray diffraction. The reactions of the η3-propargyl/allenyl complexes with Brønsted acids, such as alcohols and acetylenes, afford the corresponding substituted allenes (RCH=C=CH2) and 1-methylalk-2-ynes (CH 3C≡CR) as organic products. The reactions of 4f-Y and 4f-La with Lewis bases, such as pyridine and THF, yield die corresponding base adducts. The adduct 4f-La · py is characterized by single-crystal X-ray diffraction, revealing an η3-coordinated propargyl/allenyl ligand. © 2008 American Chemical Society.
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Het boek ‘3D Printing with biomaterials’ introduceert een manier om een duurzame en circulaire economie te realiseren; 3D printen gecombineerd met het gebruik van biomaterialen.
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In recent years, the number of human-induced earthquakes in Groningen, a large gas field in the north of the Netherlands, has increased. The majority of the buildings are built by using unreinforced masonry (URM), most of which consists of cavity (i.e. two-leaf) walls, and were not designed to withstand earthquakes. Efforts to define, test and standardize the metal ties, which do play an important role, are valuable also from the wider construction industry point of view. The presented study exhibits findings on the behavior of the metal tie connections between the masonry leaves often used in Dutch construction practice, but also elsewhere around the world. An experimental campaign has been carried out at Delft University of Technology to provide a complete characterization of the axial behavior of traditional connections in cavity walls. A large number of variations was considered in this research: two embedment lengths, four pre-compression levels, two different tie geometries, and five different testing protocols, including monotonic and cyclic loading. The experimental results showed that the capacity of the connection was strongly influenced by the embedment length and the geometry of the tie, whereas the applied pre-compression and the loading rate did not have a significant influence.
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