Br-X bonds

The broken bonds (boldface = dissociated fragment) BDEs (boldface = recommended data reference in parentheses) Methods (reference in  

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I > Br > Cl > F. In nucleophilic aromatic substitution, the formation of the addition intermediate is usually the rate-determining step so the ease of C—X bond breaking does not affeet the rate. When this is the ease, the order of reactivity is often F > Cl > Br > I. This order is the result of the polar effeet of the halogen. The stronger bond dipoles assoeiated with the more eleetronegative halogens favor the addition step and thus inerease the overall rate of reaetion. 

Using the carbon atom covalent radius 0.77 A and the covalent radii given in Figure 19-3, predict the C—X bond length in each of the following molecules CF<, CBr4, CI4. Compare your calculated bond lengths with the experimental values C—F in CF4 = 1.32 A, C—Br in CBr = 1.94 A, C—I in CI4 = 2.15 A. 

Thus the products are determined by the strength of the C—X bond for X = Cl, Br, or I the rate of aromatization (k2) appears to be sufficiently high to compete with the reverse reaction (k t). 

Reductive methods form B—B bonds from B—X bonds. For B2X4 (X = Cl, Br, I) from BXj, an electric discharge is supplemented by the presence of a metal, or metal atoms, as halide scavenger. The passage of BX3 at low pressure through a rf discharge in the presence of Hg produces the diboron tetrahalides B2X4 at 300 mg h ... 

The mechanism for this insertion of magnesium is beyond the scope of this course, and therefore, we will not go into it. For now, we should just know that we can insert Mg into a C—X bond (where X is Cl, Br, or 1). Here are some examples ... 

Let us consider the general trends of the reactivity of C-C, C-S, and C-Q (Q = Cl, Br, I) bonds towards oxidative addition and reductive elimination (Scheme 7-25). In many cases, either C-C bond-forming reductive elimination from a metal center (a) or the oxidative addition of a C-Q bond to a low-valent metal center is a thermodynamically favorable process (c). On the other hand, the thermodynamics of the C-S bond oxidative addition and reductive elimination (b) lies in between these two cases. In other words, one could more easily control the reaction course by the modulation of metal, ligand, and reactant Further progress for better understanding of S-X bond activation will be achieved by thorough stoichiometric investigations and computational studies. 

Halogen % -bonding to benzene ring i Distances to six ring carbons k Distances to two carbon atoms 1 Distance from Br to aromatic plane m C-Br - X angle... 

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