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Concerted reaction, definition

Concerted reaction, definition, 175 Coordination compounds, chemical bonds, 149-153... [Pg.162]

The term stereoselective is often confused with the term stereospecific, and the literature abounds with views as to the most satisfactory definition. To offer some clarification, it is perhaps timely to recall a frequently used term, introduced a decade or so ago, namely the stereoelectronic requirements of a reaction. All concerted reactions (i.e. those taking place in a synchronised process of bond breaking and bond forming) are considered to have precise spatial requirements with regard to the orientation of the reactant and reagent. Common examples are SN2 displacement reactions (e.g. Section 5.10.4, p. 659), E2 anti) elimination reactions of alkyl halides (e.g. Section 5.2.1, p.488), syn (pyrolytic) elimination reactions (Section 5.2.1, p.489), trans and cis additions to alkenes (e.g. Section 5.4.5, p. 547), and many rearrangement reactions. In the case of chiral or geometric reactants, the stereoisomeric nature of the product is entirely dependent on the unique stereoelectronic requirement of the reaction such reactions are stereospecific. [Pg.14]

In addition, with the implementation of metals and the use of a variety of enophiles (RCHO, O2, PTAD, RNO, Se02, R COR", benzyne, etc.), there is evidence for many of these reactions to be stepwise and oftentimes very difficult to distinguish concerted reactions from stepwise reactions. The broader definition of a radical, stepwise or concerted process of the Alder-Ene reaction will be utilized here. [Pg.3]

The aminoacyl-tRNA ligases, of course, provide the mechanism by which an amino add is activated in the presence of ATP and an activating em me specie for that amino add. The reaction is a reversible one, and can be diagramm as follows [reaction (I)], bearing in mind that our former colleague Robert Loftfield may be correct in regarding the path from free amino acid to aminoacyl-tRNA in some instances to represent a concerted reaction mechanism, without a definitive intermediate. [Pg.304]

Pericyclic reactions were defined in 1969 by R. B. Woodward and R. Hoffmann as reactions in which all first-order change.s in bonding relationships take place in concert on a closed curve that is, as concerted reactions in which all bonds are formed or brokeasimultaneously around a circle. This definition arose from the systematic study of the conservation of orbital symmetry in a series of reactions electrocyclic reactions, cycloadditions, sigmatropic shifts, cheletropic reactions, and group transfer and elimination reactions. Excellent reviews on the historical evolution of pericyclic reactions have been published. ... [Pg.2030]

The forward direction is defined with the A-B bond plain, i.e., A-B is broken in the reaction. The plain bonds (Figure 3) are understood as reactant bonds, the dashed bonds those of the product. This allows easy definition of either reactant or product from the reaction logo. If a given reaction is drawn in this convention with its shell bonds oriented as in Figure I and a dashed bond appears at the top, it represents the reverse direction of the convention, the bond being formed between A and B. Mechanism arrows are unnecessary and may be drawn in either direction, although for non-concerted reactions one may be preferable. Conventionally they are placed within the cycle. [Pg.2387]

A concerted reaction is one in which the conversion of reactants (R) into the products (P) occurs directly by way of a single transition state (T.S.). An exothermic concerted reaction is represented by the potential energy profile of Fig. 3.1(a). When the conversion of reactants into products proceeds by way of more than one transition state, such that one or more intermediates (I) are formed, the processes are accordingly non-concerted. A two-step process involving one (metastable) intermediate is represented by Fig. 3.1(b). However, since each elementary step of any chemical reaction must be concerted, by definition, then case (b) may be divided into the two concerted sequences ... [Pg.63]

In a definitive study of butadiene s reaction with l,l-dichloro-2,2-difluoio-ethylene, Bartlett concluded that [2+4] adducts of acyclic dienes with fluorinated ethylenes are formed through a mixture of concerted and nonconcerted, diradical pathways [67] The degree of observed [2+4] cycloaddition of fluorinated ethylenes IS related to the relative amounts of transoid and cisoid conformers of the diene, with very considerable (i.e., 30%) Diels-Alder adduct being observed in competition with [2+2] reaction, for example, in the reaction of 1,1 -dichloro-2,2-difluoro-ethylene with cyclopentadiene [9, 68]... [Pg.818]

Butadiene has also been reported to form a [4 + 2] cycloaddition-like product at the Si(l 11)—7 x 7 surface. Theoretically, the reaction has been predicted to occur between a rest atom-adatom pair via a step-wise, diradical path pathway that is unactivated [19,249]. Recent STM studies of butadiene adsorbed on Si(l 11)—7 x 7 have observed the formation of either a [4+ 2]-like or a [2+ 2]-like product with the Si adatom-rest atom pair, but were not able to definitely assign the product as one or the other [250]. Interestingly, the STM images also reveal that about a third of the cycloaddition product forms between two Si adatoms. Because both adatoms are positively charged, the stepwise reaction does not seem likely, and the authors suggest that this reaction occurs in a concerted fashion [250]. [Pg.360]

Olefins can add to double bonds in a reaction different from those discussed in 5-15, which, however, is still formally the addition of RH to a double bond. This reaction is called the ene synthesis44,1 and bears a certain similarity to the Diels-Alder reaction (5-47). For the reaction to proceed without a catalyst, one of the components must be a reactive dienophile (see 5-47 for a definition of this word) such as maleic anhydride, but the other (which supplies the hydrogen) may be a simple alkene such as propene. There has been much discussion of the mechanism of this reaction, and both concerted pericyclic (as shown above) and stepwise mechanisms have been suggested. The reaction between maleic anhydride and optically active PhCHMeCH=CH2 gave an optically active product,441 which is strong evi-... [Pg.794]

In reactions of mechanistic borderline, the reaction pathway may not follow the minimum energy path, but the reaction proceeds via unstable species on the PES. In other cases, the reacting system remains on the IRC but does not become trapped in the potential energy minimum. In some cases, intermediates are formed in reactions that should be concerted, whereas in other reactions a concerted TS gives an intermediate. Thus, the question of concerted versus stepwise appears too simple and the definition of concerted and stepwise reactions becomes unclear. In some reactions, the post-TS dynamics do not follow IRCs, and path bifurcation gives two types of products through a common TS. [Pg.218]

Although such a definition is seemingly quite clear and unique, the practical exploitation of the above criterion is complicated by the fact that the scission and formation of bonds is a microscopic process, inaccessible to direct experimental observation. This, of course, suggests the necessity of searching other, more easily exploitable, criteria of concert. One such criterion is the remarkable stereospecificity accompanying the formation of products in allowed pericyclic reactions [60,61]. The fact that the origin of the synchronisation in the process of scission and the formation of the bonds was always intuitively related to a certain energetic stabilisation led to another widespread opinion that all allowed reactions are automatically concerted. On the other hand nonconcertedness, advocated by frequently observed stereo-randomization [60] was practically always expected in forbidden reactions. [Pg.7]


See other pages where Concerted reaction, definition is mentioned: [Pg.163]    [Pg.55]    [Pg.29]    [Pg.178]    [Pg.281]    [Pg.72]    [Pg.300]    [Pg.259]    [Pg.266]    [Pg.3]    [Pg.1178]    [Pg.425]    [Pg.659]    [Pg.1124]    [Pg.119]    [Pg.374]    [Pg.3]    [Pg.15]    [Pg.21]    [Pg.340]    [Pg.327]    [Pg.327]    [Pg.926]    [Pg.227]   
See also in sourсe #XX -- [ Pg.605 ]

See also in sourсe #XX -- [ Pg.425 ]

See also in sourсe #XX -- [ Pg.389 , Pg.396 , Pg.1031 ]

See also in sourсe #XX -- [ Pg.605 ]

See also in sourсe #XX -- [ Pg.529 ]

See also in sourсe #XX -- [ Pg.63 , Pg.144 ]




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