Proposed reaction mechanisms

For a proposed reaction mechanism to be valid the sum of its elementary steps must equal the equation for the overall reaction and the mechanism must be consistent with all experimental observations The S l mechanism set forth m Figure 4 6 satisfies the first criterion What about the second d... 

After deposition of 0.5 nm of copper onto plasma modified polyimide, the peaks due to carbon atoms C8 and C9 and the oxygen atoms 03 and 04 were reduced in intensity, indicating that new states formed by the plasma treatment were involved in formation of copper-polyimide bonds instead of the remaining intact carbonyl groups. Fig. 28 shows the proposed reaction mechanism between copper and polyimide after mild plasma treatment. 

After metallization of the plasma-modified polyimide, there were a number of peaks in the TOF-SIMS spectra that confirmed the existence of Cu-N bonds as required by the proposed reaction mechanism (see Fig. 28). The most significant... 

A unique method to generate the pyridine ring employed a transition metal-mediated 6-endo-dig cyclization of A-propargylamine derivative 120. The reaction proceeds in 5-12 h with yields of 22-74%. Gold (HI) salts are required to catalyze the reaction, but copper salts are sufficient with reactive ketones. A proposed reaction mechanism involves activation of the alkyne by transition metal complexation. This lowers the activation energy for the enamine addition to the alkyne that generates 121. The transition metal also behaves as a Lewis acid and facilitates formation of 120 from 118 and 119. Subsequent aromatization of 121 affords pyridine 122. 

Proposed reaction mechanisms have suggested that in many rate processes the nature of the conducting species may change during the course of decomposition. There is evidence [364] that, even in the absence of pyrolysis, the conducting entity may vary with the physical form of the reactant. 

No single criterion has been recognized as constituting a satisfactory basis for the systematic classification of the kinetics of solid-phase reactions (Chapt. 1, Sect. 3). A classification based on the anion is preferred here since it is this constituent which undergoes breakdown in most reactions of interest and proposed reaction mechanisms for substances containing a common anion often include similar features. 

Characteristically, the mechanisms formulated for azide decompositions involve [693,717] exciton formation and/or the participation of mobile electrons, positive holes and interstitial ions. Information concerning the energy requirements for the production, mobility and other relevant properties of these lattice imperfections can often be obtained from spectral data and electrical measurements. The interpretation of decomposition kinetics has often been profitably considered with reference to rates of photolysis. Accordingly, proposed reaction mechanisms have included consideration of trapping, transportation and interactions between possible energetic participants, and the steps involved can be characterized in greater detail than has been found possible in the decompositions of most other types of solids. 

To verify that a proposed reaction mechanism agrees with experimental data, we construct the overall rate law implied by the mechanism and check to see whether it is consistent with the experimentally determined rate law. However, although the constructed rate law and the experimental rate law may be the same, the proposed mechanism may still he incorrect because some other mechanism may also lead to the same rate law. Kinetic information can only support a proposed mechanism it can never prove that a mechanism is correct. The acceptance of a suggested mechanism is more like the process of proof in an ideal court of law than a proof in mathematics, with evidence being assembled to give a convincing, consistent picture. 

Amidinate complexes of copper(I) and copper(II) have been found to catalyze the polymerization of carbodiimides. The copper catalysts are highly active even under air and oxygen. It was shown that the catalytic activity of an air-stable copper(II) amidinato complex is almost equal to that of reported air-sensitive titanium(IV) amidinate initiators. Scheme 225 illustrates the proposed reaction mechanism. ... 

Fig. 11. Proposed reaction mechanism for the SbaR bond cleavage reaction...

Fig. 13. Proposed reaction mechanism for ACS. The reaction involves the sequential assembly of acetyl-CoA from a carbonyl, methyl, and CoA. We favor a Ni(l) nucleophile to form a catEdytically competent paramagnetic M-CO complex, but see text for discussion of Em alternative mechanism.

The proposed reaction mechanism, which is assisted by Periasamy s stoichiometric reaction [111-118], is shown in Scheme 36. Initially, the reaction of [Fe3(CO)i2]... 

Figure 10. Proposed reaction mechanism for NO reduction by CH in the presence of O2 ...

The proposed reaction mechanism involves intermolecular nucleophilic addition of the amido ligand to the olefin to produce a zwitterionic intermediate, followed by proton transfer to form a new copper amido complex. Reaction with additional amine (presnmably via coordination to Cn) yields the hydroamination prodnct and regenerates the original copper catalyst (Scheme 2.15). In addition to the NHC complexes 94 and 95, copper amido complexes with the chelating diphosphine l,2-bis-(di-tert-bntylphosphino)-ethane also catalyse the reaction [81, 82]. 

Both heterogeneous and homogeneous catalysts have been found which allow the hydroamination reaction to occur. For heterogeneously catalyzed reactions, it is very difficult to determine which type of activation is involved. In contrast, for homogeneously catalyzed hydroaminations, it is often possible to determine which of the reactants has been activated (the unsaturated hydrocarbon or the amine) and to propose reaction mechanisms (catalytic cycles). 

The proposed reaction mechanism (Scheme 7-2) comprises (1) oxidative addition of ArSH to RhCl(PPh3)3 to give Rh(H)(Cl)(SPh)(PPli3)n, (2) coordination ofalkyne to the Rh complex, (3) ris-insertion of alkyne into the Rh-H bond with Rh positioned at terminal carbon and H at internal carbon, (4) reductive elimination of 16 from the Rh(III) complex to regenerate the Rh(I) complex. 

These arguments can be summarized in the following proposed reaction mechanism for CO oxidation at potentials anodic of the bending point ... 

Scheme 3.4 Proposed reaction mechanism for the deprotection and solvolytic rearrangement reactions of pHP caged phosphates like HPDP consistent with the TR, fs-TA and fs-KTRF experiments described here and in references 49 and 134.

Based on the data listed in Table 20.1, a value of 0.42% P was calculated for an anchored catalyst having three triphenylphosphine ligands, 0.28% P with two phosphine groups and 0.14% with one triphenylphosphene. An analytical value of 0.37% P was found which indicates that all three triphenyl-phosphines (TPP) are present in the catalyst as depicted by 4 in Scheme 20.2. However, only 0.11% P was found in the catalyst sample taken after catalyst pre-hydrogenation indicating that only one TPP is present on the active entity. Because of steric constraints between the bulky TPP and the HP A, it would appear that the TPP should be in the axial position as in 5. A proposed reaction mechanism for the anchored Wilkinson based on that shown in Scheme 20.1 is shown in Scheme 20.2. 

Figure 5 Proposed reaction mechanism, and products observed.

On the basis of i.r. spectroscopic investigations the authors concluded that in compounds of the latter type the carbonyls are cis to one another, in agreement with the proposed reaction mechanism. However it could not be shown unambiguously whether the absolute configuration is cis,cis or cis,trans. 

Figure 4.12 Schematic representation of the proposed reaction mechanism for overall photocatalytic water splitting using 03 - redox mediator and a mixture of Pt-Ti02-anatase and Ti02-rutile photocatalysts. Adapted from [161] (2001) with permission from Elsevier.

Basic Assumptions Involved in the Derivation of a Rate Expression from a Proposed Reaction Mechanism... 

Preliminary Criteria for Testing a Proposed Reaction Mechanism— Stoichiometry and Derivation of a Rate Expression for the Mechanism... 

The fact that compounds having similar chemical structures often react in similar ways implies that they follow corresponding mechanisms in proceeding from reactants to products. One must have a very sound basis in experimental fact to be able to defend successfully a proposed reaction mechanism that contains elementary reactions that represent a major departure from those accepted by the scientific community as being a proper mechanistic interpretation of related reactions. On occasions such departures are necessary, and they themselves may provide the key to an improved understanding of the common family of related reactions. 

Radkiewicz et al.184 explored the mechanism of aspartic acid racemization by means of the DFT(B3LYP)/SCRF calculations. The DFT/SCRF calculations provided quantitative rationalization of the rapid racemization observed at succinimide residues in proteins. The proposed reaction mechanism was supported by the computed increase of the acidity of the succinimide residue in aqueous solution compared to gas phase. 

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