Catalysis complexation between

Xenon difluoride [4, 5, 7, 8,10] is a white crystalline material obtained through the combination of fluorine and xenon m the presence of light The reagent is commercially available and possesses a relatively long shelf-life when stored cold (freezer) Xenon difluoride is very effective for small-scale fluormation of alkenes and activated nucleophilic substrates. The reactions are usually conducted between 0 °C and room temperature in chloroform or methylene chloride solutions Hydrogen fluoride catalysis is sometimes helpful Xenon difluoride reacts in a manner that usually involves some complexation between the substrate and reagent followed by the formation of radical and radical cation intermediates... 

Catalysis at interfaces between two immiscible liquid media is a rather wide topic extensively studied in various fields such as organic synthesis, bioenergetics, and environmental chemistry. One of the most common catalytic processes discussed in the literature involves the transfer of a reactant from one phase to another assisted by ionic species referred to as phase-transfer catalyst (PTC). It is generally assumed that the reaction process proceeds via formation of an ion-pair complex between the reactant and the catalyst, allowing the former to transfer to the adjacent phase in order to carry out a reaction homogeneously [179]. However, detailed comparisons between interfacial processes taking place at externally biased and open-circuit junctions have produced new insights into the role of PTC [86,180]. 

A second ternary complex reaction mechanism is one in which there is a compulsory order to the substrate binding sequence. Reactions that conform to this mechanism are referred to as bi-bi compulsory ordered ternary complex reactions (Figure 2.13). In this type of mechanism, productive catalysis only occurs when the second substrate binds subsequent to the first substrate. In many cases, the second substrate has very low affinity for the free enzyme, and significantly greater affinity for the binary complex between the enzyme and the first substrate. Thus, for all practical purposes, the second substrate cannot bind to the enzyme unless the first substrate is already bound. In other cases, the second substrate can bind to the free enzyme, but this binding event leads to a nonproductive binary complex that does not participate in catalysis. The formation of such a nonproductive binary complex would deplete the population of free enzyme available to participate in catalysis, and would thus be inhibitory (one example of a phenomenon known as substrate inhibition see Copeland, 2000, for further details). When substrate-inhibition is not significant, the overall steady state velocity equation for a mechanism of this type, in which AX binds prior to B, is given by Equation (2.16) ... 

The use of the symbol E in 5.1 for the environment had a double objective. It stands there for general environments, and it also stands for the enzyme considered as a very specific environment to the chemical interconversion step [102, 172], In the theory discussed above catalysis is produced if the energy levels of the quantum precursor and successor states are shifted below the energy value corresponding to the same species in a reference surrounding medium. Both the catalytic environment E and the substrates S are molded into complementary surface states to form the complex between the active precursor complex Si and the enzyme structure adapted to it E-Si. In enzyme catalyzed reactions the special productive binding has been confussed with the possible mechanisms to attain it lock-key represents a static view while the induced fit concept... 

The cationic polymerisation of olefins by metal halides has been interpreted in two ways. The first theory, proposed by Hunter and Yohe [1], ascribed the catalysis to the formation of a polarised complex between the metal halide and the olefin ... 

That the formation of molecular complexes (especially EDA complexes) can catalyse the decomposition of the cr-adduct has been discussed in Section n.E. Another possibility is that the substrate and catalyst (nucleophile or added base) form a complex which is then attacked by a new molecule of the nucleophile in this context catalysis need no longer be associated with proton removal. Thus, Ryzhakov and collaborators183 have recently shown that the N-oxides of 4-chloropyridine and 4-chloroquinoline act as jt-donors toward tetracyanoethylene and that the reactions of these substrates with pyridine and quinoline are strongly catalysed by the jr-acceptor. Similarly, the formation of a Meisenheimer complex between 1,3,5-trinitrobenzene and l,8-diazabicyclo[5,4,0]undec-7-ene in toluene has been assumed to take place via an association complex to explain the observed second-order in tertiary amine184. 

Catalysis by DABCO in the reactions of FDNB with piperidine, r-butylamine, aniline, p-anisidine and m-anisidine (usually interpreted as base catalysis as in Section B) was also assumed to occur by the formation of a complex between DABCO and the substrate14913. The high (negative) p-value of —4.88 was deemed inappropriate for the usually accepted mechanism of the base-catalysed step (reaction 1). For the reactions with p-chloroaniline, m- and p-anisidines and toluidines in benzene in the presence of DABCO a p-value of —2.86 was found for the observed catalysis by DABCO (fc3DABC0). The results were taken to imply that the transition state of the step catalysed by DABCO and that of the step catalysed by the nucleophile have similar requirements, and in both the nucleophilic (or basicity) power of the nucleophile is involved. This conclusion is in disagreement with the usual interpretation of the base-catalysed step. 

A series of 3-alkyl- and 3-aryl-7/7-furo[3,2- ]-l-benzopyran-7-ones 78 (linear furocoumarins) was synthesized and evaluated for their photochemical and nonphotochemical crosslink formation with DNA as well as for their spectro-photometric and fluorescent properties, lipophilicity, and ability to photobleach A, A -dimethyl-/)-nitrosoaniline (RNO) after irradiation with UVA light <2002AP187>. The synthesis of the linear furocoumarins (Scheme 10) was a modification of a previously published method in which 7-hydroxy-2//-l-benzopyran-2-ones 76 were converted into / -ketoethers 77 by alkylation with haloketones under phase-transfer catalysis conditions. Base-catalyzed intramolecular condensation and subsequent acidification gave the corresponding 78. A molecular complex between each one of these fluorescent furocoumarins and DNA was observed, but only compounds with a 3-Me or 3-Ph group showed UVA irradiation-induced crosslink formation. 

We believe that catalysis occurs by formation of a complex between acetaldehyde, peracetic acid, and the metal ion in the 3+ oxidation state. The metal ion could be acting as a superacid as for peracetic acid decomposition, although oxidation-reduction reactions within the complex cannot be ruled out. Here again, we have found a disturbing lack of catalytic activity of other trivalent metals (aluminum, iron, and chromium). Simple acid catalysis is not as effective as proved when using p-toluenesulfonic acid and acetyl borate. This indicates that at least more than one coordination position is needed to obtain a complex of the proper configuration. 

Figure 1. Catalysis and template action of RNA and proteins. Catalytic action of one RNA molecule on another one is shown in the simplest case, the "hammerhead ribozyme." The substrate is a tridecanucleotide forming two double-helical stacks together with the ribozyme (n = 34) in the confolded complex. Tertiary interactions determine the detailed structure of the hammerhead ribozyme complex and are important for the enzymatic reaction cleaving one of the two linkages between the two stacks. Substrate specificity of ribozyme catalysis is caused by secondary structure in the cofolded complex between substrate and catalyst. Autocatalytic replication of oligonucleotide and nucleic acid is based on G = C and A = U complementarity in the hydrogen bonded complexes of nucleotides forming a Watson-Crick type double helix. Gunter von Kiedrowski s experi-...

Phenylacetylene did not form an adduct under similar conditions. The complex between 1,2-bis(dimethylphosphino)-1,2-dicarbaclosododeca-borane with nickel(II) chloride effectively catalyzed the hydrosilylation of olefins (209). Catalysis by this nickel complex differed, however, in that considerable amounts of internal adducts were formed ... 

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