Search for a trans-Disulfide: Structural Analysis of Di-tert-adamantyl Disulfide by Photoelectron Spectroscopy, Derivation of σI (t-Ad), and Molecular Mechanics Calculations for Related Bulky Disulfides

Research output: Contribution to journal › Journal article › Research › peer-review

Standard

Search for a trans-Disulfide : Structural Analysis of Di-tert-adamantyl Disulfide by Photoelectron Spectroscopy, Derivation of σI (t-Ad), and Molecular Mechanics Calculations for Related Bulky Disulfides. / Jørgensen, Flemming S.; Snyder, James P.

In: Journal of Organic Chemistry, Vol. 45, No. 6, 01.01.1980, p. 1015-1020.

Research output: Contribution to journal › Journal article › Research › peer-review

Harvard

Jørgensen, FS & Snyder, JP 1980, 'Search for a trans-Disulfide: Structural Analysis of Di-tert-adamantyl Disulfide by Photoelectron Spectroscopy, Derivation of σI (t-Ad), and Molecular Mechanics Calculations for Related Bulky Disulfides', Journal of Organic Chemistry, vol. 45, no. 6, pp. 1015-1020. https://doi.org/10.1021/jo01294a020

APA

Jørgensen, F. S., & Snyder, J. P. (1980). Search for a trans-Disulfide: Structural Analysis of Di-tert-adamantyl Disulfide by Photoelectron Spectroscopy, Derivation of σI (t-Ad), and Molecular Mechanics Calculations for Related Bulky Disulfides. Journal of Organic Chemistry, 45(6), 1015-1020. https://doi.org/10.1021/jo01294a020

Vancouver

Jørgensen FS, Snyder JP. Search for a trans-Disulfide: Structural Analysis of Di-tert-adamantyl Disulfide by Photoelectron Spectroscopy, Derivation of σI (t-Ad), and Molecular Mechanics Calculations for Related Bulky Disulfides. Journal of Organic Chemistry. 1980 Jan 1;45(6):1015-1020. https://doi.org/10.1021/jo01294a020

Author

Jørgensen, Flemming S. ; Snyder, James P. / Search for a trans-Disulfide : Structural Analysis of Di-tert-adamantyl Disulfide by Photoelectron Spectroscopy, Derivation of σI (t-Ad), and Molecular Mechanics Calculations for Related Bulky Disulfides. In: Journal of Organic Chemistry. 1980 ; Vol. 45, No. 6. pp. 1015-1020.

Bibtex

@article{4e6230dcf7f04a21bd8070b56d7d35e8,
title = "Search for a trans-Disulfide: Structural Analysis of Di-tert-adamantyl Disulfide by Photoelectron Spectroscopy, Derivation of σI (t-Ad), and Molecular Mechanics Calculations for Related Bulky Disulfides",
abstract = "Photoelectron spectroscopy of t-Ad-SS-t-Ad yields an IE(n) - IE(n+) energy difference of 0.51 eV at the frontier orbital gap suggesting to an S-S dihedral angle of θ(CSSC) = 103°. Molecular mechanics calculations with Allinger's MMI yield a shallow energy minimum with respect to rotation about the S-S bond. Two conformations differing by 0.7 kcal/mol are located at θ(CSSC) = 100 and 114°. Regression analysis of dialkyl disulfide ionization energies and substituent inductive parameters (σI) leads to σ(t-Ad) = -0.089, indicating t-Ad to be a better electron donor than t-Bu. Finally force field calculations for several sterically congested disulfides suggest that trans disulfides may be realizable for very large alkyl substituents such as the (t-Bu)3C, polymethyladamantyl, and trimethylperhydrotriquinicenyl moieties.",
author = "J{\o}rgensen, {Flemming S.} and Snyder, {James P.}",
year = "1980",
month = jan,
day = "1",
doi = "10.1021/jo01294a020",
language = "English",
volume = "45",
pages = "1015--1020",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "6",

}

RIS

TY - JOUR

T1 - Search for a trans-Disulfide

T2 - Structural Analysis of Di-tert-adamantyl Disulfide by Photoelectron Spectroscopy, Derivation of σI (t-Ad), and Molecular Mechanics Calculations for Related Bulky Disulfides

AU - Jørgensen, Flemming S.

AU - Snyder, James P.

PY - 1980/1/1

Y1 - 1980/1/1

N2 - Photoelectron spectroscopy of t-Ad-SS-t-Ad yields an IE(n) - IE(n+) energy difference of 0.51 eV at the frontier orbital gap suggesting to an S-S dihedral angle of θ(CSSC) = 103°. Molecular mechanics calculations with Allinger's MMI yield a shallow energy minimum with respect to rotation about the S-S bond. Two conformations differing by 0.7 kcal/mol are located at θ(CSSC) = 100 and 114°. Regression analysis of dialkyl disulfide ionization energies and substituent inductive parameters (σI) leads to σ(t-Ad) = -0.089, indicating t-Ad to be a better electron donor than t-Bu. Finally force field calculations for several sterically congested disulfides suggest that trans disulfides may be realizable for very large alkyl substituents such as the (t-Bu)3C, polymethyladamantyl, and trimethylperhydrotriquinicenyl moieties.

AB - Photoelectron spectroscopy of t-Ad-SS-t-Ad yields an IE(n) - IE(n+) energy difference of 0.51 eV at the frontier orbital gap suggesting to an S-S dihedral angle of θ(CSSC) = 103°. Molecular mechanics calculations with Allinger's MMI yield a shallow energy minimum with respect to rotation about the S-S bond. Two conformations differing by 0.7 kcal/mol are located at θ(CSSC) = 100 and 114°. Regression analysis of dialkyl disulfide ionization energies and substituent inductive parameters (σI) leads to σ(t-Ad) = -0.089, indicating t-Ad to be a better electron donor than t-Bu. Finally force field calculations for several sterically congested disulfides suggest that trans disulfides may be realizable for very large alkyl substituents such as the (t-Bu)3C, polymethyladamantyl, and trimethylperhydrotriquinicenyl moieties.

UR - http://www.scopus.com/inward/record.url?scp=0007438193&partnerID=8YFLogxK

U2 - 10.1021/jo01294a020

DO - 10.1021/jo01294a020

M3 - Journal article

AN - SCOPUS:0007438193

VL - 45

SP - 1015

EP - 1020

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 6

ER -

ID: 218715279