Thermodynamic data for hydrogen bonding of thiols with Lewis bases in carbon tetrachloride. Weak association by the PMR method

Hu, Siung J.; Goldberg, Edward B.; Miller, Sidney I.

doi:10.1002/mrc.1270040508

Cited by 10 publications

(4 citation statements)

References 28 publications

(7 reference statements)

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“…The stoichiometry for the washed n -dodecanethiol-ligated QBs, {CdSe[ n -dodecanethiol] 0.26±0.02 }, is right on the ideal value for L-type ligation of only the 3-coordinate surface Cd atoms. This is consistent with the weak hydrogen-like bonding expected for thiols, − such that the putatively H-bonded thiol ligands are removed by washing. The compositions determined for the {CdSe[ n -C 12 H 25 S] 0.23±0.02 [Na] 0.23±0.02 } and {CdSe[Cd( n -dodecanethiolate) 2 ] 0.22±0.02 } QBs are also consistent with one X-type and one Z-type ligand per 3-coordinate surface Cd and Se atom, respectively.…”

Section: Discussionsupporting

confidence: 78%

Thiol Versus Thiolate Ligation on Cadmium Selenide Quantum Belts

Yao

Buhro

2019

Chem. Mater.

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Addition of thiols to semiconductor nanocrystals influences their photoluminescence efficiencies; however, the mode of ligationas neutral thiol ligands or as anionic thiolate ligandsis rarely clearly established. We now differentiate these ligation modes on wurtzite CdSe quantum belts (QBs). n-Dodecanethiol and n-dodecanethiolate ligations of CdSe QBs are obtained through ligand exchanges. Reaction of {CdSe[Cd(oleate)2]0.19} QBs and sodium n-dodecanethiolate affords {CdSe[n-C12H25S]0.23[Na]0.23} QBs, having bound-ion-pair X-type ligation. Reaction of {CdSe[Cd(oleate)2]0.19} QBs and n-dodecanethiol affords {CdSe[Cd(n-dodecanethiolate)2]0.22} QBs, having Cd(n-dodecanethiolate)2 ligands as Z-type ligation. {CdSe[Cd(n-dodecanethiolate)2]0.22} QBs are also prepared by reaction of {CdSe[n-octylamine]0.53} QBs and Cd(n-dodecanethiolate)2. Reaction of {CdSe[Br]0.1[(n-octyl)4N]0.1} QBs and n-dodecanethiol affords {CdSe[n-dodecanethiol]0.26} QBs, having L-type ligation. {CdSe[n-dodecanethiol]0.26} QBs are also prepared by reaction of {CdSe[n-C12H25S]0.23[Na]0.23} or {CdSe[Cd(n-dodecanethiolate)2]0.22} QBs with n-dodecanethiol. Thus, interchange of n-dodecanethiol and n-dodecanethiolate ligation is readily achieved.

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Section: Discussionsupporting

confidence: 78%

Thiol Versus Thiolate Ligation on Cadmium Selenide Quantum Belts

Yao

Buhro

2019

Chem. Mater.

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“…For n -BuSH and t -BuSH, K assoc values with DMSO are 0.17 (at 307 K) and 0.30 (at 305 K) L mol -1 , respectively,28b an order opposite to the order of the p K a 's of the thiols 28b. The acidity of 12 is probably higher than that of the aliphatic thiols and closer to that of thiophenol.…”

Section: Discussionmentioning

confidence: 88%

“…The K assoc value for 12 with DMSO (0.087 L mol -1 ) is of the same order of magnitude as the very few K assoc values available for the aliphatic and aromatic thiols. For n -BuSH and t -BuSH, K assoc values with DMSO are 0.17 (at 307 K) and 0.30 (at 305 K) L mol -1 , respectively,28b an order opposite to the order of the p K a 's of the thiols 28b.…”

Section: Discussionmentioning

confidence: 88%

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Triphenylethenethiol. Structure, Equilibria with the Thioketone, Solvation, and Association with DMSO

Selzer

Rappoport

1996

J. Org. Chem.

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The simple thioenols, triphenylethenethiol (12) and 2,2-diphenyl-1-anisylethenethiol (13) were prepared. Both are the only observed constituent of the thioenol ⇌ thioketone equilibria and comparison and estimation suggested that the thiocarbonyl ⇌ thioenol equilibrium constant K enol for 12 and other simple thioenols is ≥106 higher than for the corresponding carbonyl ⇌ enol equilibria. The X-ray diffraction of 12, which is the first measured for a simple thioenol, shows a propeller arrangment of the three rings. The δ(SH) in the 1H NMR spectrum increases with the increase in the hydrogen bonding accepting parameter β of the solvent. The association constant K assoc of 12 with DMSO is 0.087, much lower than values of triarylethenols with DMSO. Reaction of diphenylacetaldehyde with Lawesson's reagent did not give the thioenol, but gave bis(2,2-diphenylvinyl) sulfide (16) and a substance (17) having a trithiaphosphorinane system.

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PMR Study of 2,6‐Ditertbutyl‐p‐cresol Hydrogen Bonding with Chloroform and Acetone

Wawer¹,

Kȩcki²

1976

Ber Bunsenges Phys Chem

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The chemical shifts of the PMR signals of the OH proton and the chloroform proton were measured in the solutions of 2,6-ditertbutylp-cresol with chloroform or acetone in cyclohexane at different temperatures. The structure of hydrogen bond complexes and the enthalpy and entropy of their formation was determined. The chemical shift dependence on temperature occured to be nonlinear. The value of the chemical shift of the OH for a given hydrogen bonded complex A,, was stated to be temperature dependent. Die chemische Verschiebung der PMR-Signale von dem OH-Proton und von dem Chloroform-Proton wurde gemessen in den Losungen von 2.6-Ditertbutyl-p-kresol mit Chloroform oder Aceton im Cyclohexan in verschiedenen Temperaturen. Die Struktur der wasserstoffbriickengebundenen Komplexe und die Enthalpie und Entropie ihrer Bildung wurde bestimmt. Die Abhangigkeit der chemischen Verschiebung von der Temperatur erschien nicht linear zu sein. Die chemische Verschiebung von O H Fur einen bestimmten wasserstoffbriickengebundenen Kompiex A,,,, erwies sich als temperaturabhangig.

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Thermodynamic data for hydrogen bonding of thiols with Lewis bases in carbon tetrachloride. Weak association by the PMR method

Cited by 10 publications

References 28 publications

Thiol Versus Thiolate Ligation on Cadmium Selenide Quantum Belts

Thiol Versus Thiolate Ligation on Cadmium Selenide Quantum Belts

Triphenylethenethiol. Structure, Equilibria with the Thioketone, Solvation, and Association with DMSO

PMR Study of 2,6‐Ditertbutyl‐p‐cresol Hydrogen Bonding with Chloroform and Acetone

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