239135-41-2Relevant articles and documents
Kinetics and mechanism of the nucleophilic substitution of tellurium(II) dialkanethiolates, Te(SR1)2 with thiols, HSR2
Fleischer, Holger
, p. 815 - 825 (2007/10/03)
The equilibrium reaction between tellurium(II) dithiolates and thiols, Te(SR1)2 + 2 HSR2 ? Te(SR 2)2 + 2 HSR1 was studied by means of 1H- and 125Te NMR spectroscopy and ab initio quantum chemical methods. It was found that the reaction is catalyzed by Bronsted acids and bases, the catalytic activity corresponding to the strength of the respective acid or base. Investigation of the initial step of the reaction, Te(SR1)2 + HSR2 ? Te(SR 1)(SR2) + HSR1, showed it to proceed according to first order kinetics for Te(SR1)2, HSR2 and for the catalyst. Ab initio geometry optimizations and frequency calculations suggest [Te(SR1)(HSR1)(HSR2)]+ and [Te(SR1)2(SR2)]- to be stable intermediates and not transition states in the acid and base catalyzed reactions, respectively. The reaction hence proceeds via an additional elimination rather than an SN2 mechanism. The catalytic activity displayed by acids and bases can be applied to reduce the temperature in synthesis of thermally labile tellurium(II) dithiolates. Copyright Taylor & Francis Inc.
