The reaction of monomeric and dimeric rhodium(I) amido complexes with unactivated olefins to generate imines is reported. Transamination of {(PEt(3))(2)RhN(SiMePh(2))(2)} (1a) or its -N(SiMe(3))(2) analogue 1b with p-toluidine gave the dimeric [(PEt(3))(2)Rh(mu-NHAr)](2) (Ar = p-tolyl) (2a) in 80% isolated yield. Reaction of 2a with PEt(3) generated the monomeric (PEt(3))(3)Rh(NHAr) (Ar = p-tolyl) (3a). PEt(3)-ligated arylamides 2a and 3a reacted with styrene to transfer the amido group to the olefin and to form the ketimine Ph(Me)C=N(p-tol) (4a) in 48-95% yields. The dinuclear amido hydride (PEt(3))(4)Rh(2)(mu-NHAr)(mu-H) (Ar = p-tolyl) (5a) was formed from reaction of 2a in 95% yield, and a mixture of this dimeric species and the (PEt(3))(n)RhH complexes with n = 3 and 4 was formed from reaction of 3a in a combined 75% yield. Propene reacted with 2a to give Me(2)C=N(p-tol) (4b) and 5a in 90 and 57% yields. Propene also reacted with 3a to give 4b and 5a in 65 and 94% yields. Analogues of 2a and 3a with varied electronic properties also reacted with styrene to form the corresponding imines, and moderately faster rates were observed for reactions of electron-rich arylamides. Kinetic studies of the reaction of 3a with styrene were most consistent with formation of the imine by migratory insertion of olefin into the rhodium-amide bond to generate an aminoalkyl intermediate that undergoes beta-hydrogen elimination to generate a rhodium hydride and an enamine that tautomerizes to the imine.
The leaf membrane lipids of many plant species, including Arabidopsis thaliana (L.) Heynh., are synthesized by two complementary pathways that are associated with the chloroplast and the endoplasmic reticulum. By screening directly for alterations in lipid acyl-group composition, we have identified several mutants of Arabidopsis that lack the plastid pathway because of a deficiency in activity of the first enzyme in the plastid pathway of glycerolipid synthesis, acyl-ACP: sn -glycerol-3-phosphate acyltransferase (EC 2.3.1.15) (where ACP is acyl carrier protein). The lesion results in an increased synthesis of lipids by the cytoplasmic pathway that largely compensates for the loss of the plastid pathway and provides nearly normal amounts of all the lipids required for chloroplast biogenesis. However, the fatty acid composition of the leaf membrane lipids of the mutants is altered because the acyltransferases associated with the two pathways normally exhibit different substrate specificities. The remarkable flexibility of the system provides an insight into the nature of the regulatory mechanisms that allocate lipids for membrane biogenesis.
No abstract is provided for this article.
Structure and bonding -- Dative liquids -- Covalent (X type) ligands bound through metal-carbon and metal-hydrogen bonds -- Covalent (X type) ligands bound through metal-heteroatom bonds -- Ligand substitution reactions -- Oxidative addition of nonpolar reagents -- Oxidative addition of polar reagents -- Reductive elimination -- Migratory insertion reactions -- Elimination reactions -- Nucleophilic attack on coordinated ligands -- Electrophilic attack on coordinated ligands -- Metal-ligand multiple bonds -- Principles of catalysis (written with Prof. Patrick J. Walsh) -- Homongeneous hydrogenation -- Hydrofunctionalization and oxidative functionalization of olefins -- Catalytic carbonylation -- Catalytic C-H functionalization -- Transition metal-catalyzed coupling reactions -- Allylic substitution -- Metathesis of olefins and alkynes -- Polymerization and oligomerization of olefins.
We introduce the concept of a photovoltaic band gap Epvg for amorphous solar cells. This is the minimum photon energy thermodynamically required for the generation, of two free carriers in an operating solar cell. For hydrogenated amorphous silicon the photovoltaic band gap is 1.57 eV at 1-sun illumination.
After demonstrating that traditional design procedures are unrealistic, a method for design of concrete gravity dams to remain essentially within the elastic range of behavior is presented. All factors that are significant in the dynamic response of dams are considered and the capacity of concrete to support dynamic stresses in tension is recognized. In designing dams for the very intense ground shaking that may occur only rarely in highly seismic areas, limited cracking of concrete may be permitted. However, at the present time it is not possible to analytically predict, with high degree of confidence, the extent of cracking and damage that a concrete gravity dam may experience during very intense ground shaking. The research needed to improve these analysis procedures and to incorporate them in the design process is identified. The procedure presented in this paper for design of concrete gravity dams to be built in seismic regions is also applicable to evaluation of the safety of existing dams.
The 11th part of our tour through one-dimensional binary Cellular Automata concerns period-2 rules, which form the second group in our classification of the 88 globally-independent CA rules according to the properties of their periodic orbits. In this article, we display the basin tree diagrams of all period-2 rules along with their time-2 characteristic functions, and then we prove that all rules belonging to group 2 have robust period-2 ω-limit orbits for any finite, and infinite, bit string length. This rigorous result, which pairs with the one about period-1 rules given in the tenth installment of our chronicle, confirms what we stated about period-2 rules on the basis of empirical evidence. In the second part of this tutorial, we introduce the notion of quasi global-equivalence and prove that there are only 82 quasi globally-independent CA rules. For the first time, we show that the space-time patterns of globally-independent local rules can depend on each other, and we present an example of quasi-global transformation. We also define the super string 𝄞, and its unique decimal representation x 𝄞 , dubbed the super decimal, which provides a completely transparent yet rigorous proof that rule [Formula: see text] is chaotic when L → ∞. Moreover, we present the basin tree generation formulas, which uncover the analytical relationships between basin trees of globally-equivalent rules. Last but not least, for pedagogical and epistemological reasons, we conclude this paper with the selection of rule[Formula: see text], instead of rule [Formula: see text], as the prototypic universal Turing machine for our future discourse.