Mechanism of proton transfer to coordinated thiolates: encapsulation of acid stabilizes precursor intermediate was written by Alwaaly, Ahmed;Clegg, William;Harrington, Ross W.;Petrou, Athinoula L.;Henderson, Richard A.. And the article was included in Dalton Transactions in 2015.Application In Synthesis of Sodium 2-methyl-2-propanethiolate This article mentions the following:
Earlier kinetic studies on the protonation of the coordinated thiolate in the square-planar [Ni(SC6H4R’-4)(triphos)]+ (R’ = NO2, Cl, H, Me or MeO) by lutH+ (lut = 2,6-dimethylpyridine) indicate a two-step mechanism involving initial formation of a (kinetically detectable) precursor intermediate, {[Ni(SC6H4R’-4)(triphos)]···Hlut}2+ (KR1), followed by an intramol. proton transfer step (kR2). The analogous [Ni(SR)(triphos)]BPh4 {R = Et, But or Cy; triphos = PhP(CH2CH2PPh2)2} were prepared and characterized by spectroscopy and x-ray crystallog. Similar to the aryl thiolate complexes, [Ni(SR)(triphos)]+ are protonated by lutH+ in an equilibrium reaction but the observed rate law is simpler. Anal. of the kinetic data for both [Ni(SR)(triphos)]+ and [Ni(SC6H4R’-4)(triphos)]+ shows that both react by the same mechanism, but that KR1 is largest when the thiolate is poorly basic, or the 4-R’ substituent in the aryl thiolates is electron-withdrawing. It is both NH···S hydrogen bonding and encapsulation of the bound lutH+ (by the Ph groups on triphos) which stabilize the precursor intermediate. In the experiment, the researchers used many compounds, for example, Sodium 2-methyl-2-propanethiolate (cas: 29364-29-2Application In Synthesis of Sodium 2-methyl-2-propanethiolate).
Sodium 2-methyl-2-propanethiolate (cas: 29364-29-2) belongs to alcohols. Similar to water, an alcohol can be pictured as having an sp3 hybridized tetrahedral oxygen atom with nonbonding pairs of electrons occupying two of the four sp3 hybrid orbitals. Under carefully controlled conditions, simple alcohols can undergo intermolecular dehydration to give ethers. This reaction is effective only with methanol, ethanol, and other simple primary alcohols.Application In Synthesis of Sodium 2-methyl-2-propanethiolate
Referemce:
Alcohol – Wikipedia,
Alcohols – Chemistry LibreTexts