A valence bond perspective of the reaction force formalism

Rincón, Luís; Torres, Javier; Mora, José R.; Zambrano, Cesar H.; Rodríguez, Vladimir

doi:10.1007/s00214-019-2538-7

Cited by 5 publications

(3 citation statements)

References 44 publications

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“…From Table 1 , it is observed that methyl dehalogenations occurring in the presence of Co II Cbx have activation energies greater than those reported for the same reactions mediated by Co I Cbx. With the purpose of unveiling the main reasons for this, an alternative interpretation of the RF, previously reported by some of the authors of the present work, is employed [ 61 ]. This RF picture requires a briefly description of the valence bond state correlation diagram (VBSCD) depicted in Scheme 3 , where it is illustrated that the energy required to promote the system from R to its excited state R* is denoted by

, and

is the quantum mechanical resonance energy that separates the crossing of the diabatic curves and the maxima of the adiabatic potential energy.…”

Section: Resultsmentioning

confidence: 99%

“…Moreover, as stated in Reference. [ 61 ], the

can be approximated to

; thus, the activation energy can be expressed as

, which, in the present study, is used to estimate the

term. It is important to point out that the reaction occurring in the presence of Co I Cbx was recalculated at the ωB97-XD/6–311++G(d,p), with the purpose to have a common base line for the comparison.…”

Section: Resultsmentioning

confidence: 99%

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A Theoretical Study of the C–X Bond Cleavage Mediated by Cob(II)Aloxime

Seijas

Zambrano²,

Rodríguez³

et al. 2022

Molecules

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The C–X bond cleavage in different methyl halides (CH3X; X = Cl, Br, I) mediated by 5,6-dimethylbenzimidazole-bis(dimethylglyoximate)cobalt(II) (CoIICbx) was theoretically investigated in the present work. An SN2-like mechanism was considered to simulate the chemical process where the cobalt atom acts as the nucleophile and the halogen as the leaving group. The reaction path was computed by means of the intrinsic reaction coordinate method and analyzed in detail through the reaction force formalism, the quantum theory of atoms in molecules (QTAIM), and the calculation of one-electron density derived quantities, such as the source function (SF) and the spin density. A thorough comparison of the results with those obtained in the same reaction occurring in presence of 5,6-dimethylbenzimidazole-bis(dimethylglyoximate)cobalt(I) (CoICbx) was conducted to reveal the main differences between the two cases. The reactions mediated by CoIICbx were observed to be endothermic and possess higher activation energies in contrast to the reactions where the CoICbx complex is present. The latter was supported by the reaction force results, which suggest a relationship between the activation energy and the ionization potentials of the different nucleophiles present in the cleavage reaction. Moreover, the SF results indicates that the lower axial ligand (i.e., 5,6-dimethylbenzimidazole) exclusively participates on the first stage of the reaction mediated by the CoIICbx complex, while for the CoICbx case, it appears to have an important role along the whole process. Finally, the QTAIM charge analysis indicates that oxidation of the cobalt atom occurs in both cases; at the same time, it suggests the formation of an uncommon two-center one-electron bond in the CoIICbx case. The latter was confirmed by means of electron localization calculations, which resulted in a larger electron count at the Co–C interatomic region for the CoICbx case upon comparison with its CoIICbx counterpart.

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, and

is the quantum mechanical resonance energy that separates the crossing of the diabatic curves and the maxima of the adiabatic potential energy.…”

Section: Resultsmentioning

confidence: 99%

“…Moreover, as stated in Reference. [ 61 ], the

can be approximated to

; thus, the activation energy can be expressed as

, which, in the present study, is used to estimate the

Section: Resultsmentioning

confidence: 99%

A Theoretical Study of the C–X Bond Cleavage Mediated by Cob(II)Aloxime

Seijas

Zambrano²,

Rodríguez³

et al. 2022

Molecules

Self Cite

View full text Add to dashboard Cite

show abstract

“…84 Once the RP is determined further insight into the reaction mechanism can be obtained by collecting and analyzing molecular properties of the RC along the RP. Some representative examples include (i) monitoring changes of the topological features of the electron density 85,86 or the electron localization function 87 along the RP [88][89][90] ; (ii) the reaction force and force constant method, which is aimed at extracting information from higher derivatives of the energy profile taken along the RP, [91][92][93] where one has to take into account that the energy is a cumulative property and as such the mechanistic information obtained is more of a holistic nature; (iii) the discussion of local reactivity descriptors, e.g., the Fukui function, and how they infer reactivity trends along the RP 94,95 ; and (iv) the recently suggested exploration of the PES with immersive virtual reality. 96 A complementary approach of monitoring the reaction mechanism is pursued in ab initio molecular dynamics (MD) simulations as to provide an atomic visualization into the detail of molecular reactions on a femtosecond time scale.…”

Section: Introductionmentioning

confidence: 99%