Oxidative addition thermodynamics

The coordination chemistry of NO is often compared to that of CO but, whereas carbonyls are frequently prepared by reactions involving CO at high pressures and temperatures, this route is less viable for nitrosyls because of the thermodynamic instability of NO and its propensity to disproportionate or decompose under such conditions (p. 446). Nitrosyl complexes can sometimes be made by transformations involving pre-existing NO complexes, e.g. by ligand replacement, oxidative addition, reductive elimination or condensation reactions (reductive, thermal or photolytic). Typical examples are ... 

The general catalytic cycle for the coupling of aryl-alkenyl halides with alkenes is shown in Fig. 9.6. The first step in this catalytic cycle is the oxidative addition of aryl-alkenyl halides to Pd(0). The activity of the aryl-alkenyl halides still follows the order RI > ROTf > RBr > RC1. The olefin coordinates to the Pd(II) species. The coordinated olefin inserts into Pd—R bond in a syn fashion, p-Hydrogen elimination can occur only after an internal rotation around the former double bond, as it requires at least one /I-hydrogen to be oriented syn perpendicular with respect to the halopalladium residue. The subsequent syn elimination yields an alkene and a hydridopalladium halide. This process is, however, reversible, and therefore, the thermodynamically more stable (E)-alkene is generally obtained. Reductive elimination of HX from the hydridopalladium halide in the presence of a base regenerates the catalytically active Pd(0), which can reenter the catalytic cycle. The oxidative addition has frequently assumed to be the rate-determining step. 

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. 

Oxidative addition of H2 and Ph3SiH to IrBr(CO)(chiraphos), where chiraphos 2,S, 3,S -bis (diphenylphosphino)butane, leads to stable kinetic (115a,115b), followed by thermodynamic (116a,116b) diastereomers as shown in reaction Scheme 15.2 3 The crystal structure of cis-[IrH2(chiraphos)2]BF4 has been reported.204... 

Cross-coupling to form carbon heteroatom bonds occurs by oxidative addition of an organic halide, generation of an aryl- or vinylpalladium amido, alkoxo, tholato, phosphido, silyl, stannyl, germyl, or boryl complex, and reductive elimination (Scheme 2). The relative rates and thermodynamics of the individual steps and the precise structure of the intermediates depend on the substrate and catalyst. A full discussion of the mechanism for each type of substrate and each catalyst is beyond the scope of this review. However, a series of reviews and primary literature has begun to provide information on the overall catalytic process.18,19,22,23,77,186... 

Sigma-bond metathesis at hypovalent metal centers Thermodynamically, reaction of H2 with a metal-carbon bond to produce new C—H and M—H bonds is a favorable process. If the metal has a lone pair available, a viable reaction pathway is initial oxidative addition of H2 to form a metal alkyl dihydride, followed by stepwise reductive elimination (the microscopic reverse of oxidative addition) of alkane. On the other hand, hypovalent complexes lack the... 

A thermodynamically stable (silyl)(stannyl)palladium(n) complex is synthesized by an oxidative addition of the Si-Sn linkage to palladium(O) (Scheme 63).267 The complex has the square-planar geometry with a m-arrangement of the silicon and tin atoms. An alkyne reacts with the complex to afford a silastannated product as a mixture of cisjtrans stereoisomers (10 1). 

The elimination of HC1 was proposed to occur also during the H2 activation with the [Pd(PNP)Cl]Cl complexes (PNP = bis-2-(diphenylphosphino)ethyl benzy-lamine, bis-2-(diphenylphosphino)ethyl amine or tris-2-(diphenylphosphino)ethyl amine) [24, 25]. Based on the findings of 31P 1H - and 1H-NMR investigations, the hydride [HPd(PNP)]Cl was detected under H2 atmosphere. The alternative mechanism which involves the oxidative addition of H2 with formation of a Pd(IV)-dihydride intermediate, appeared less likely on the basis of thermodynamic considerations. 

With Pd(0) generated in situ, the oxidative addition of aryl bromide 102 to Pd(0) proceeds to form Pd(II) intermediate 104. Migratory insertion of 104 then occurs to furnish the cyclized indoline intermediate 105. Subsequent reductive elimination of 105 takes place in a cis fashion, giving rise to exo-cyclic olefin 107, which then tautomerizes spontaneously to the thermodynamically more stable indole 103. The reductive elimination by-product as a palladium hydride species 106 reacts with base, regenerating Pd(0) to close the catalytic cycle. 

The transfer of the silyl ligand onto the a-carbon of the substrate is followed by the formation of an intermediate in which the (1-phenylethyl)trichlorosilane product still weakly coordinated in a rj2-fashion. The corresponding endo and exo intermediates (11a and lib, respectively) are 3.5 and 4.2 kcal/mol, respectively, more stable than the endo 7i-complex, 8a Therefore the exo-stereoisomer is again thermodynamically more stable than the endo form. Finally, the oxidative addition of a molecule of trichlorosilane occurs with concomitant liberation of the products. The formation of both R and S products is exothermic by -20 kcal/mol. 

In order to get a catalytic cycle it is necessary that the metal sulfide intermediate can react with hydrogen to form the reduced metal complex (or compound) and H2S. For highly electropositive metals (non-noble metals) this is not possible for thermodynamic reasons. The co-ordination chemistry and the oxidative addition reactions that were reported mainly involved metals such as ruthenium, iridium, platinum, and rhodium. 

Reaction (9) generates methyl iodide for the oxidative addition, and reaction (10) converts the reductive elimination product acetyl iodide into the product and it regenerates hydrogen iodide. There are, however, a few distinct differences [2,9] between the two processes. The thermodynamics of the acetic anhydride formation are less favourable and the process is operated much closer to equilibrium. (Thus, before studying the catalysis of carbonylations and carboxylations it is always worthwhile to look up the thermodynamic data ) Under standard conditions the AG values are approximately ... 

These findings have stimulated enormously the search for intermolecular activation of C-H bonds, in particular those of unsubstituted arenes and alkanes. In 1982 Bergman [2] and Graham [3] reported on the reaction of well-defined complexes with alkanes and arenes in a controlled manner. It was realised that the oxidative addition of alkanes to electron-rich metal complexes could be thermodynamically forbidden as the loss of a ligand and rupture of the C-H bond might be as much as 480 kl.mol, and the gain in M-H and M-C... 

Another effective way of staying clear of the thermodynamic barriers of C-H activation/substitution is the use of the c-bond metathesis reaction as the crucial elementary step. This mechanism avoids intermediacy of reactive metal species that undergo oxidative additions of alkanes, but instead the alkyl intermediate does a o-bond metathesis reaction with a new substrate molecule. Figure 19.13 illustrates the basic sequence [20],... 

A subsequent study using neopentane as the alkane substrate gave evidence in support of the same mechanism, and also allowed resolution of near-coincident y(CO) absorptions due to [Cp Rh(CO)Kr] (1946 cm ) and [Cp Rh(CO)(di2-neopen-tane)] (1947 cm ) [18]. Further studies were able to quantify the reactivity of [Cp Rh(CO)Kr] towards a range of alkanes [20]. It was found that binding of the alkane to Rh becomes more favorable, thermodynamically, as the alkane size is increased, but that the rate of the C-H oxidative addition step shows less variation with linear alkane chain length. No reaction with methane was observed, which was explained by the ineffective binding of methane (relative to excess Kr) to Rh. 

The reductive elimination has been less studied than the oxidative addition and migratory insertion steps. Forster reported that [Rh(C(0)Me)(CO)l3f decomposed to Acl and [Rh(CO)2l2] in several solvents without any marked dependence of the rate on the solvent. Acl was detected in aprotic media from reaction of Mel with CO in the presence of [Rh(CO)2l2r. However, it was also concluded that oxidative addition of AcX to [Rh(CO)2X2] (X = Cl, Br) was not thermodynamically favorable [34]. 

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