Reactive site

When the Pts island adsorbs onto a metallic or bimetallic surface tensile strain develops in the island strain and a concomitant compressive strain develops on the substrate surface in a local neigh- 

Ground State Struetures and Energies for Complexes and Adduets 1-24 Shown in Fig. 1. m = 2 S + 1, is the Multiplieity, with S the Total Eleetron Spin of the Moleeule i-j is The Bond Length Between Atoms i and j. 

The development of strain on X -Pts occurs concurrently with the relaxation to equilibrium of the distance between X and Pts. In fact, relative to the interlayer distance in tlie Xbuik crystal, the island-support distance (Table 2) decreases by 6% in CosPt-Pts and 2% in Pte-Pt3, but increases by 2% in Co3-Pt3, 3% in Nis-Pts, 4% in Fes-Pts and 11% in Pts-Pts. These on average island-substrate equilibrium distances as well as tensile and compressive strains may be considered as upper bounds for those observed at the interface of Pts with the Xbuik substrates. 

Electronic and Geometric Stmetnre Parameters for Pt3 in a [Xbuik-XsJ-Pts Snbstrate-Island System. 

Support metal, Xbuik Support sample, X, t -band center (eV) Xs-Pt3 binding energy (eV/atom) Distance to support surface (A) 

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Numerous m.o.-theoretical calculations have been made on quinoline and quinolinium. Comparisons of the experimental results with the theoretical predictions reveals that, as expected (see 7.2), localisation energies give the best correlation. jr-Electron densities are a poor criterion of reactivity in electrophilic substitution the most reactive sites for both the quinolinium ion and the neutral molecule are predicted to be the 3-, 6- and 8-positions. ... 

All of the material in this text and most of chemistry generally can be understood on the basis of what physicists call the electromagnetic force Its major principle is that opposite charges attract and like charges repel As you learn organic chemistry a good way to start to connect structure to properties such as chemical reactivity is to find the positive part of one molecule and the neg ative part of another Most of the time these will be the reactive sites... 

FIGURE 18 5 The reactive sites in aldol addition are the carbonyl group of one aldehyde mole cule and the a carbon atom of another... 

Molecular orbitals are useful tools for identifying reactive sites m a molecule For exam pie the positive charge m allyl cation is delocalized over the two terminal carbon atoms and both atoms can act as electron acceptors This is normally shown using two reso nance structures but a more compact way to see this is to look at the shape of the ion s LUMO (the LUMO is a molecule s electron acceptor orbital) Allyl cation s LUMO appears as four surfaces Two surfaces are positioned near each of the terminal carbon atoms and they identify allyl cation s electron acceptor sites... 

Liquid coating resins are prepared by reacting methanol or butanol with the initial hydroxyme-thylureas. Ether exchange reactions between the amino resin and the reactive sites on the polymer produce a cross-linked film. 

Fig. 13. Polymerization chemistry of phenol—formaldehyde condensation synthesis of novolac resia. The phenol monomer(s) are used ia stoichiometric excess to avoid geUation, although branching iavariably occurs due to the multiple reactive sites on the aromatic ring.

Rea.ctlons, Propargyl alcohol has three reactive sites—a primary hydroxyl group, a triple bond, and an acetylenic hydrogen—making it an extremely versatile chemical intermediate. 

Methylbutynol. 2-Methyl-3-butyn-2-ol [115-19-5] prepared by ethynylation of acetone, is the simplest of the tertiary ethynols, and serves as a prototype to illustrate their versatile reactions. There are three reactive sites, ie, hydroxyl group, triple bond, and acetylenic hydrogen. Although the triple bonds and acetylenic hydrogens behave similarly in methylbutynol and in propargyl alcohol, the reactivity of the hydroxyl groups is very different. 

The chemistry of melamines and phenoHcs is quite similar. In both cases formaldehyde [50-00-0] is added to the reactive sites on the patent ring to form methylol phenols (3) or methylol melamines (4) (see Phenolresins Aminoresins). There ate six reactive sites on the triazine ring of melamine [108-78-1] (1) so it is possible to form hexamethylolmelamine. However, the most common degree of methylolation is 1.5—2.0. The ortho and para positions of phenol ate active thus phenol can be trimethylolated (2). However, as with melamine, lower degrees of methylolation such as 1.2—2.5 ate... 

Substitution Reactions on Side Chains. Because the benzyl carbon is the most reactive site on the propanoid side chain, many substitution reactions occur at this position. Typically, substitution reactions occur by attack of a nucleophilic reagent on a benzyl carbon present in the form of a carbonium ion or a methine group in a quinonemethide stmeture. In a reversal of the ether cleavage reactions described, benzyl alcohols and ethers may be transformed to alkyl or aryl ethers by acid-catalyzed etherifications or transetherifications with alcohol or phenol. The conversion of a benzyl alcohol or ether to a sulfonic acid group is among the most important side chain modification reactions because it is essential to the solubilization of lignin in the sulfite pulping process (17). 

Chemical Properties. Higher a-olefins are exceedingly reactive because their double bond provides the reactive site for catalytic activation as well as numerous radical and ionic reactions. These olefins also participate in additional reactions, such as oxidations, hydrogenation, double-bond isomerization, complex formation with transition-metal derivatives, polymerization, and copolymerization with other olefins in the presence of Ziegler-Natta, metallocene, and cationic catalysts. All olefins readily form peroxides by exposure to air. 

Amides in general are stable to elevated processing temperatures, ak oxidation, and dilute acids and bases. StabiUty is reduced in amides containing unsaturated alkyl chains unsaturation offers reactive sites for many reactions. 

Aniline—formaldehyde resins were once quite important because of their excellent electrical properties, but their markets have been taken over by newer thermoplastic materials. Nevertheless, some aniline resins are stiU. used as modifiers for other resins. Acrylamide (qv) occupies a unique position in the amino resins field since it not only contains a formaldehyde reactive site, but also a polymerizable double bond. Thus it forms a bridge between the formaldehyde condensation polymers and the versatile vinyl polymers and copolymers. 

Reaction with vatious nucleophilic reagents provides several types of dyes. Those with simple chromophores include the hernicyanine iodide [16384-23-9] (20) in which one of the terminal nitrogens is nonheterocyclic enamine triearbocyanine iodide [16384-24-0] (21) useful as a laser dye and the merocyanine [32634-47-2] (22). More complex polynuclear dyes from reagents with more than one reactive site include the trinuclear BAB (Basic-Acidic-Basic) dye [66037-42-1] (23) containing basic-acidic-basic heterocycles. Indolizinium quaternary salts (24), derived from reaction of diphenylcyclopropenone [886-38-4] and 4-picoline [108-89-4] provide trimethine dyes such as (25), which absorb near 950 nm in the infrared (23). 

Double-Bond Cure Sites. The effectiveness of this kind of reactive site is obvious. It allows vulcanization with conventional organic accelerators and sulfur-based curing systems, besides vulcanization by peroxides. Fast and controllable vulcanizations are expected so double-bond cure sites represent a chance to avoid post-curing. Furthermore, blending with other diene elastomers, such as nitrile mbber [9003-18-3] is gready faciUtated. 

Prior to butyl mbber, the known natural and synthetic elastomers had reactive sites at every monomer unit. Unlike natural mbber, polychloroprene, and polybutadiene, butyl mbber had widely spaced olefin sites with aHyUc hydrogens. This led to the principle of limited functionahty synthetic elastomers that was later appHed to other synthetic elastomers, eg, chlorosulfonated polyethylene, siUcone mbber, and ethylene—propylene terpolymers. 

Cross-linking reactions for the polyisobutylene-type polymers depend on adding a reactive site, usually an aHyUc hydrogen or halogen. These reactive sites allow vulcanization with sulfur and accelerators or metal oxides (76,77). 

Monooximes of a-diketones have found applicability in the synthesis of 2-aminopyrazine 1-oxides by condensation with a-aminonitriles, and this reaction was used by White and coworkers in an approach to the synthesis of Cypridina etioluciferamine (Scheme 66 R = 3-indoloyl) (73T3761). In this instance, the use of TiCU as a catalyst was essential, since the carbonyl group in 3-acylindoles is normally deactivated and the required amine/carbonyl condensation is impractically slow. Under normal circumstances the carbonyl group in simple alkyl-substituted monoximes of a-diketones is the more reactive site and the reaction is rapid, requiring no catalysis (69LA(726)loo). 

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