Working Paper Article Version 3 This version is not peer-reviewed

Second Derivative as a Function of the Transition State and Noncovalent Interactions: Implementation of Graphic Methodology in Electrophilic Aromatic Substitution Mechanistic Analysis

Version 1 : Received: 16 April 2021 / Approved: 19 April 2021 / Online: 19 April 2021 (11:32:42 CEST)
Version 2 : Received: 24 May 2021 / Approved: 24 May 2021 / Online: 24 May 2021 (14:55:32 CEST)
Version 3 : Received: 16 June 2021 / Approved: 21 June 2021 / Online: 21 June 2021 (14:08:50 CEST)
(This article belongs to the Research Topic Quantum Computing)

How to cite: Cerkovnik, J.; Stamenković, N. Second Derivative as a Function of the Transition State and Noncovalent Interactions: Implementation of Graphic Methodology in Electrophilic Aromatic Substitution Mechanistic Analysis. Preprints 2021, 2021040463 Cerkovnik, J.; Stamenković, N. Second Derivative as a Function of the Transition State and Noncovalent Interactions: Implementation of Graphic Methodology in Electrophilic Aromatic Substitution Mechanistic Analysis. Preprints 2021, 2021040463

Abstract

To date, theoretical analyses have provided several useful methods/algorithms for studying transition states and non-covalent interactions. Potential Energy Scan (PES) is one such method that has found wide application in the physicochemical community. Analyzing the PES profiles of the catalytic system of FeBr3 in Electrophilic Aromatic Substitution (EAS) with molecular halogens, one can notice an obvious difference from the modern textbook mechanisms proposed in this area of study. Moreover, the newly presented Graphic Methodology (GM) allows a simple and reliable transition state determination even for very weakly bound charge transfer complexes using second-order derivatives as an efficient tool in the graphical analysis. Relative errors that can be reduced to a few parts per thousand in transition state estimation make this method a potentially very useful tool in further graphical studies of non-covalent interactions. Studies performed using high-precision semiempirical methods suggest that the process of halonium ion quenching proceeds along a completely different pathway, suggesting a possible novel transition metal-nonmetal catalytic system involved in the EAS electrophilic quenching step. The results presented here strongly suggest a future GM application that is widely used and the introduction of pseudo and pre-transition states as new terms in the description of non-covalent interactions.

Subject Areas

Second-Order Derivative (SOD) method; Graphic method; Potential Energy Scan (PES); Charge-Transfer complex; Iron(III) bromide; Iron(V) complex; Transition metal-halogen tandem catalysis

Comments (1)

Comment 1
Received: 21 June 2021
Commenter: Janez Cerkovnik
Commenter's Conflict of Interests: Author
Comment: The title and abstract were changed to point out the Graphic Method development and its application in this paper. Paper is sent to another journal.
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