The RS-·HSR Hydrogen Bond: Acidities of α,ω-Dithiols and Electron Affinities of Their Monoradicals
- 15 September 2001
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 123 (40) , 9800-9805
- https://doi.org/10.1021/ja0039684
Abstract
Gas-phase acidities (deltaGo(acid)) have been measured for 1,2-ethanedithiol, 1,3-propanedithiol, and 1,4-butanedithiol, using a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Adiabatic electron affinities (EAs) of the thiolate monoradicals of these compounds were assigned from electron photodetachment spectra of their corresponding thiolate monoanions, acquired using a cw-ICR. The dithiols exhibit enhanced acidities (up to 8.7 kcal/mol in deltaGo(acid)) and greater EAs (up to 6.7 kcal/mol) than analogous monothiol species. These differences are attributed to an intramolecular RS-.HSR hydrogen bond in the thiolate anion. Considerations of the RO-.HOR hydrogen bond in monoanions of alpha,omega-diols and in the [CH(3)O-.HOCH(3)] complex anion suggest that the RS-.HSR hydrogen bond provides up to 9 kcal/mol extra stabilization.Keywords
This publication has 15 references indexed in Scilit:
- Transient Hydrogen Atom Adducts to Disulfides. Formation and EnergeticsJournal of the American Chemical Society, 2000
- Crystal structures of reduced, oxidized, and mutated human thioredoxins: evidence for a regulatory homodimerStructure, 1996
- Gas-phase acidities of diolsJournal of the American Society for Mass Spectrometry, 1993
- Thermodynamics of the association reactions hydroxide + water = (HOHOH)- and methoxy(1-) + methanol = (CH3OHOCH3)- in the gas phaseThe Journal of Physical Chemistry, 1990
- Dimethyl disulfide: anion-molecule reactions in the gas phase at 300 KJournal of the American Chemical Society, 1989
- Relative acidities of water and methanol and the stabilities of the dimer anionsThe Journal of Physical Chemistry, 1986
- Anion-alcohol hydrogen bond strengths in the gas phaseJournal of the American Chemical Society, 1984
- Gas phase negative ion chemistry of alkylchloroformates. A convenient method for bimolecular generation of chloride ion adducts and determination of chloride affinities from ion cyclotron resonance thermal equilibrium measurementsCanadian Journal of Chemistry, 1984
- Electron photodetachment from mercaptyl anions (RS-). Electron affinities of mercaptyl radicals and the sulfur-hydrogen bond strength in mercaptansJournal of the American Chemical Society, 1980
- Hydrogen Bonds Involving Sulfur. II. The Hydrogen Sulfide–Hydrosulfide ComplexThe Journal of Chemical Physics, 1971