Exploring borderline S1-S2 mechanisms: the role of explicit solvation protocols in the DFT investigation of isopropyl chloride
Nucleophilic substitution at saturated carbon is a crucial class of organic reactions, playing a pivotal role in various chemical transformations that yield valuable compounds for society. Despite the well-established S N 1 and S N 2 mechanisms, secondary substrates, particularly in solvolysis react...
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Published in | RSC advances Vol. 14; no. 7; pp. 4692 - 471 |
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Main Authors | , , , |
Format | Journal Article |
Published |
05.02.2024
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Abstract | Nucleophilic substitution at saturated carbon is a crucial class of organic reactions, playing a pivotal role in various chemical transformations that yield valuable compounds for society. Despite the well-established S
N
1 and S
N
2 mechanisms, secondary substrates, particularly in solvolysis reactions, often exhibit a borderline pathway. A molecular-level understanding of these processes is fundamental for developing more efficient chemical transformations. Typically, quantum-chemical simulations of the solvent medium combine explicit and implicit solvation methods. The configuration of explicit molecules can be defined through top-down approaches, such as Monte Carlo (MC) calculations for generating initial configurations, and bottom-up methods that involve user-dependent protocols to add solvent molecules around the substrate. Herein, we investigated the borderline mechanism of the hydrolysis of a secondary substrate, isopropyl chloride (
i
PrCl), at DFT-M06-2X/aug-cc-pVDZ level, employing explicit and explicit + implicit protocols. Top-down and bottom-up approaches were employed to generate substrate-solvent complexes of varying number (
n
= 1, 3, 5, 7, 9, and 12) and configurations of H
2
O molecules. Our findings consistently reveal that regardless of the solvation approach, the hydrolysis of
i
PrCl follows a loose-S
N
2-like mechanism with nucleophilic solvent assistance. Increasing the water cluster around the substrate in most cases led to reaction barriers of Δ
H
‡
21 kcal mol
−1
, with nine water molecules from MC configurations sufficient to describe the reaction. The More O'Ferrall-Jencks plot demonstrates an S
N
1-like character for all transition state structures, showing a clear merged profile. The fragmentation activation strain analyses indicate that energy barriers are predominantly controlled by solvent-substrate interactions, supported by the leaving group stabilization assessed through CHELPG atomic charges.
We explored borderline S
N
X
reactions quantum-chemically, revealing a preferred dissociative-S
N
2 pathway controlled by solute-solvent interactions through various solvation models. |
---|---|
AbstractList | Nucleophilic substitution at saturated carbon is a crucial class of organic reactions, playing a pivotal role in various chemical transformations that yield valuable compounds for society. Despite the well-established S
N
1 and S
N
2 mechanisms, secondary substrates, particularly in solvolysis reactions, often exhibit a borderline pathway. A molecular-level understanding of these processes is fundamental for developing more efficient chemical transformations. Typically, quantum-chemical simulations of the solvent medium combine explicit and implicit solvation methods. The configuration of explicit molecules can be defined through top-down approaches, such as Monte Carlo (MC) calculations for generating initial configurations, and bottom-up methods that involve user-dependent protocols to add solvent molecules around the substrate. Herein, we investigated the borderline mechanism of the hydrolysis of a secondary substrate, isopropyl chloride (
i
PrCl), at DFT-M06-2X/aug-cc-pVDZ level, employing explicit and explicit + implicit protocols. Top-down and bottom-up approaches were employed to generate substrate-solvent complexes of varying number (
n
= 1, 3, 5, 7, 9, and 12) and configurations of H
2
O molecules. Our findings consistently reveal that regardless of the solvation approach, the hydrolysis of
i
PrCl follows a loose-S
N
2-like mechanism with nucleophilic solvent assistance. Increasing the water cluster around the substrate in most cases led to reaction barriers of Δ
H
‡
21 kcal mol
−1
, with nine water molecules from MC configurations sufficient to describe the reaction. The More O'Ferrall-Jencks plot demonstrates an S
N
1-like character for all transition state structures, showing a clear merged profile. The fragmentation activation strain analyses indicate that energy barriers are predominantly controlled by solvent-substrate interactions, supported by the leaving group stabilization assessed through CHELPG atomic charges.
We explored borderline S
N
X
reactions quantum-chemically, revealing a preferred dissociative-S
N
2 pathway controlled by solute-solvent interactions through various solvation models. |
Author | Peixoto, Bárbara Pereira Fiorot, Rodolfo Goetze de Andrade, Karine Nascimento Carneiro, José Walkimar de Mesquita |
AuthorAffiliation | Department of Inorganic Chemistry Department of Organic Chemistry Universidade Federal Fluminense (UFF) Chemistry Institute |
AuthorAffiliation_xml | – name: Department of Organic Chemistry – name: Universidade Federal Fluminense (UFF) – name: Department of Inorganic Chemistry – name: Chemistry Institute |
Author_xml | – sequence: 1 givenname: Karine Nascimento surname: de Andrade fullname: de Andrade, Karine Nascimento – sequence: 2 givenname: Bárbara Pereira surname: Peixoto fullname: Peixoto, Bárbara Pereira – sequence: 3 givenname: José Walkimar de Mesquita surname: Carneiro fullname: Carneiro, José Walkimar de Mesquita – sequence: 4 givenname: Rodolfo Goetze surname: Fiorot fullname: Fiorot, Rodolfo Goetze |
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DOI | 10.1039/d4ra00066h |
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References_xml | – issn: 2022 issue: vol. 18 end-page: p 53-121 publication-title: Annual Reports in Computational Chemistry doi: Xu Coote – issn: 2009 publication-title: Gaussian 09, Revision E.01 doi: Frisch Trucks Schlegel Scuseria Robb Cheeseman Scalmani Barone Mennucci Petersson Nakatsuji Caricato Li Hratchian Izmaylov Bloino Zheng Sonnenberg Frisch Trucks Schlegel Scuseria Robb Cheeseman Scalmani Barone Mennucci Petersson Nakatsuji Caricato Li Hratchian Izmaylov Bloino Zheng Sonnenberg Hada Ehara Toyota Fukuda Hasegawa Ishida Nakajima Honda Kitao Nakai Vreven Montgomery Peralta Jr Ogliaro Bearpark Heyd Brothers Kudin Staroverov Kobayashi Normand Raghavachari Rendell Burant Iyengar Tomasi Cossi Rega Millam Klene Knox Cross Bakken Adamo Jaramillo Gomperts Stratmann Yazyev Austin Cammi Pomelli Ochterski Martin Morokuma Zakrzewski Voth Salvador Dannenberg Dapprich Daniels Farkas Foresman Ortiz Cioslowski Fox – issn: 1997 publication-title: Physical Chemistry: A Molecular Approach doi: McQuarrie Simon – issn: 2007 publication-title: Advanced Organic Chemistry - Part A: Structure and Mechanisms doi: Carey Sundberg |
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Title | Exploring borderline S1-S2 mechanisms: the role of explicit solvation protocols in the DFT investigation of isopropyl chloride |
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