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The chemical reactivity of the first- and second-generation Grubbs catalysts has always been a significant issue in olefin metathesis. In the present work, we study the [2+2] cycloreversion/cycloaddition and the alkylidene rotation involved into the interconversion of the ruthenacyclobutane intermediate, through the reaction force and reaction force constant analysis. It has been found that the structural contribution controls the barrier energy in the interconversion of ruthenacyclobutane via [2+2] cycloreversion/cycloaddition, which is slightly lower in the second generation of Grubbs catalysts while its electronic contribution is slightly higher, which unveils a major rigidity and donor/acceptor properties of the NHC. This finding explains a greater structural contribution in the rate constant. Moreover, on the basis of the reaction force constant, the process can be classified as "two-stage"-concerted reactions, noting a more asynchronous process when the first generation is used as a catalyst. Finally, a similar analysis into the alkylidene rotation was performed. It was determined that [2+2] cycloreversion and alkylidene rotations take place in a sequential manner, the energy barrier is again controlled by structural reorganization, and the pathway is less asynchronous. [ABSTRACT FROM AUTHOR]

A synchronous, concerted chemical process is rigorously divided by the reaction force F( R), the negative gradient of V( R), into 'reactant' and 'product' regions which are dominated by structural changes and an intervening 'transition' region which is electronically intensive. The reaction force constant κ( R), the second derivative of V( R), is negative throughout the transition region, not just at the nominal transition state, at which κ( R) has a minimum. This is consistent with experimental evidence that there is a transition region, not simply a specific point. We show graphically that significant nonsynchronicity in the process is associated with the development of a maximum of κ( R) in the transition region, which increases as the process becomes more nonsynchronous. (We speculate that for a nonconcerted process this maximum is actually positive.) Thus, κ( R) can serve as an indicator of the level of nonsynchronicity. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

The reaction force F( ξ) is the negative gradient of the potential energy of a chemical process along the intrinsic reaction coordinate ξ. We extend the rigorous concept of F( ξ) to the 'activation strain model' of Bickelhaupt et al., to formulate the 'strain' force F( ξ) that retards a reaction and the 'interaction' force F( ξ) that drives it. These are investigated for a group of Diels-Alder cycloadditions. The results fully support the interpretation of the minimum of F( ξ) as defining the beginning of the transition from deformed reactants to eventual products. [ABSTRACT FROM AUTHOR]

We have analyzed the variation of the reaction force F( ξ) and the reaction force constant κ( ξ) along the intrinsic reaction coordinates ξ of the water-assisted proton transfer reactions of HX-N = Y (X,Y = O,S). The profile of the force constant of the vibration associated with the reactive mode, k( ξ), was also determined. We compare our results to the corresponding intramolecular proton transfers in the absence of a water molecule. The presence of water promotes the proton transfers, decreasing the energy barriers by about 12 - 15 kcal mol. This is due in part to much smaller bond angle changes being needed than when water is absent. The κ( ξ) profiles along the intrinsic reaction coordinates for the water-assisted processes show striking and intriguing differences in the transition regions. For the HS-N = S and HO-N = S systems, two κ( ξ) minima are obtained, whereas for HO-N = O only one minimum is found. The k( ξ) show similar behavior in the transition regions. We propose that this fine structure reflects the degree of synchronicity of the two proton migrations in each case. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]