The mechanism and heterodinuclear cooperative effects for AgRu-catalyzed alkyne semihydrogenation were analyzed with density-functional theory (DFT) and experiment. This combined effort revealed the following: (1) AgRucatalyzed diphenylacetylene hydrogenation initially gives a kinetic mixture of cis-stilbene and trans-stilbene by an ionic Ag−H hydride transfer transition state and post-transition state bifurcation, which was identified by quasiclassical direct dynamics simulations. (2) The hydrogenation reaction exhibits an unexpected inverse kinetic isotope effect (KIE < 1) resulting from an inverse equilibrium isotope effect (EIE) for heterodinuclear H 2 /D 2 activation. (3) The Ag−Ru heterodinuclear cooperative effective is critical for both H 2 activation and vinylsilver protonolysis reaction steps. ( 4) Rate studies and computational analysis show that electron-donating groups accelerate catalysis.

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No abstract

This chapter examines the role of culture in parenting. Although successful parenting involves the use of many skills, cultural and otherwise, rituals provide a blueprint that parents, generation after generation, can and have used to influence their children to emulate proper social behavior. Rituals are used to teach children not only what the behavioral codes are, but how to interpret and respond appropriately to social cues. These parental tactics, to the extent they remain traditional, also teach children why they should transmit the same strategies to their own offspring and thus how to perpetuate the behavior into future generations. After discussing parenting in more detail, the chapter focuses on language, which is central to teaching and learning and the foundation on which parents influence their children.

dihydroxyanthracenes, obtained by the action of Grignard reagents upon anthraquinone, can be conveniently reduced by phenylhydrazine in acetic acid to 9 : 10-disubstituted anthracenes in good yield. 9 : ~~-DI-(~-CARBOXYALI3), and the consequent production of bridges across the 9 : 10-positions of anthracene ( 11), but no general method for the synthesis of such acids has been published.The reaction of 9 : 10-dihydro-9 : 10-disodioanthracene with a-halogeno-esters failed to produce any hydrolysable material, possibly because of acylation of the disodio-compound analogous to that reported for ethyl benz0ate.l Clearly, a halide is required which bears on the a-position a relatively inert system which is capable of being converted into a carboxy-group. Ally1 bromide has been employed successfully to give a 35% yield of 9 : 10-diallyl-9 : 10-dihydroanthracene. However, oxidation of this compound to 9 : 10-diallylanthracene, by the use of benzoquinone or chloranil, gave only very poor yields.Accordingly, Grignard reagents bearing a-olefinic and a-ethereal groups, capable of further reaction, have been examined for activity towards anthraquinone, and a study made of the reduction of the 9 : 10-disubstituted 9 : 10-dihydro-9 : 10-dihydroxyanthracenes so obtained. The method of Cook et aL2 for the reaction of anthraquinone with twice the calculated quantity of Grignard reagents gave reproducible yields of the desired diols. Hitherto, the most generally successful reduction of such diols has been to shake their dimethyl ethers with an alkali metal for several days.3 This method failed with 9 : 10-diallyl-9 : 10-diethoxy-9 : 10-dihydroanthracene, potassium or sodium being used, but it was found that such diols, or their ethereal derivatives, could be reduced smoothly by phenylhydrazine in acetic acid in 8 hr. The yields of 9 : 10-disubstituted anthracenes (111) from diprimary alkylanthracenediols are of the order of 60%. 9 : 10-Diallyl-9 : 10-dihydro-9 : 10-dihydroxyanthracene, prepared by Cook et aL2 in unquoted yield, was obtained in 73% yield from allylmagnesium bromide, and found to exist in two isomeric forms, which were easily separated after methylation or ethylation. Both diethyl derivatives absorb at 10.09 p and 10-95 p (allyl), and at 9.4 p (ethoxy). The mixture of diallylanthracenediols, and both dimethyl and diethyl ethers, reacted with phenylhydrazine in acetic acid to give a 65%. yield of 9 : 10-diallylanthracene, absorbing at 10.09 p and 10-95 p (allyl), and identical with the product obtained from 9 : 10-dihydro-9 : 10-disodioanthracene. The best results were obtained by mixing the reactants in the cold, warming the solution rapidly until nitrogen was evolved, and finally refluxing for 4 hr. Addition of the diol to a boiling solution of phenylhydrazine in acetic acid lowered the yield to 31%, and the major product was a yelIow powder, m. p. 195"; the spectral and