Density functional theory gas- and solution-phase study of nucleophilic substitution at di- and trisulfides

Steven M. Bachrach; Joseph M. Hayes; Trang Dao; Justin L. Mynar

doi:10.1007/s00214-002-0323-4

Density functional theory gas- and solution-phase study of nucleophilic substitution at di- and trisulfides

Steven M. Bachrach, Joseph M. Hayes, Trang Dao, Justin L. Mynar

Research output: Contribution to journal › Article › peer-review

31 Scopus citations

Abstract

Density functional calculations indicate that nucleophilic substitution in the thiolate-disulfide and thiolate-trisulfide exchange reactions proceeds by an addition-elimination pathway. Solution calculations were performed using B3LYP/6-31 + G* and the polarized continuum method. These solution-phase calculations indicate that for the reactions where the sulfur under attack bears a hydrogen atom, the substitution proceeds via an addition-elimination mechanism; however, when a methyl group is attached to the sulfur under attack, the S_N2 mechanism is predicted.

Original language	English (US)
Pages (from-to)	266-271
Number of pages	6
Journal	THEORETICAL CHEMISTRY ACCOUNTS
Volume	107
Issue number	5
DOIs	https://doi.org/10.1007/s00214-002-0323-4
State	Published - 2002
Externally published	Yes

Keywords

DFT
Disulfide
Nucleophilic substitution
Solvent effects
Trisulfide

ASJC Scopus subject areas

Physical and Theoretical Chemistry

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10.1007/s00214-002-0323-4

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title = "Density functional theory gas- and solution-phase study of nucleophilic substitution at di- and trisulfides",

abstract = "Density functional calculations indicate that nucleophilic substitution in the thiolate-disulfide and thiolate-trisulfide exchange reactions proceeds by an addition-elimination pathway. Solution calculations were performed using B3LYP/6-31 + G* and the polarized continuum method. These solution-phase calculations indicate that for the reactions where the sulfur under attack bears a hydrogen atom, the substitution proceeds via an addition-elimination mechanism; however, when a methyl group is attached to the sulfur under attack, the SN2 mechanism is predicted.",

keywords = "DFT, Disulfide, Nucleophilic substitution, Solvent effects, Trisulfide",

author = "Bachrach, {Steven M.} and Hayes, {Joseph M.} and Trang Dao and Mynar, {Justin L.}",

year = "2002",

doi = "10.1007/s00214-002-0323-4",

language = "English (US)",

volume = "107",

pages = "266--271",

journal = "THEORETICAL CHEMISTRY ACCOUNTS",

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TY - JOUR

T1 - Density functional theory gas- and solution-phase study of nucleophilic substitution at di- and trisulfides

AU - Bachrach, Steven M.

AU - Hayes, Joseph M.

AU - Dao, Trang

AU - Mynar, Justin L.

PY - 2002

Y1 - 2002

N2 - Density functional calculations indicate that nucleophilic substitution in the thiolate-disulfide and thiolate-trisulfide exchange reactions proceeds by an addition-elimination pathway. Solution calculations were performed using B3LYP/6-31 + G* and the polarized continuum method. These solution-phase calculations indicate that for the reactions where the sulfur under attack bears a hydrogen atom, the substitution proceeds via an addition-elimination mechanism; however, when a methyl group is attached to the sulfur under attack, the SN2 mechanism is predicted.

AB - Density functional calculations indicate that nucleophilic substitution in the thiolate-disulfide and thiolate-trisulfide exchange reactions proceeds by an addition-elimination pathway. Solution calculations were performed using B3LYP/6-31 + G* and the polarized continuum method. These solution-phase calculations indicate that for the reactions where the sulfur under attack bears a hydrogen atom, the substitution proceeds via an addition-elimination mechanism; however, when a methyl group is attached to the sulfur under attack, the SN2 mechanism is predicted.

KW - DFT

KW - Disulfide

KW - Nucleophilic substitution

KW - Solvent effects

KW - Trisulfide

UR - http://www.scopus.com/inward/record.url?scp=84962339125&partnerID=8YFLogxK

U2 - 10.1007/s00214-002-0323-4

DO - 10.1007/s00214-002-0323-4

M3 - Article

AN - SCOPUS:84962339125

SN - 1432-881X

VL - 107

SP - 266

EP - 271

JO - THEORETICAL CHEMISTRY ACCOUNTS

JF - THEORETICAL CHEMISTRY ACCOUNTS

IS - 5

ER -

Density functional theory gas- and solution-phase study of nucleophilic substitution at di- and trisulfides

Abstract

Keywords

ASJC Scopus subject areas

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