95334-06-8Relevant academic research and scientific papers
Reactions at highly sterically hindered organosilicon centres. Chemistry of (Me3Si)3CSiPhHI, (Me3Si)3CSiPh(OMe)I, and related species
Aiube, Zakariah H.,Eaborn, Colin
, p. 159 - 169 (2007/10/02)
The iodide TsiSiPhHI (Tsi = (Me3Si)3C) has been shown to react with a range of silver(I) salts, AgY, to give the corresponding species TsiSiPhHY; the reactions with AgOCN give either the isocyanate alone or a mixture of this with the normal cyanate, depen
Effects of the substituents Y in reactions of compounds of the type (Me3Si)3CSiH(C6H4Y-p)I. Evidence against the SN2(intermediate) mechanism for methanolysis of (Me3Si)3CSiMe2I and (Me3Si)3CSiHPhI
Azarian, Davoud B.,Eaborn, Colin,Lickiss, Paul D.
, p. 255 - 262 (2007/10/02)
The rates of methanolysis of the iodides TsiSiH(C6H4Y-p)I (Y MeO, Me, H, Cl, or CF3) in 1/1 v/v MeOH/dioxane have been shown to be increased by electron withdrawal by Y and correspondingly decreased by electron release. This is taken to imply that the methanol is covalently involved in the transition state, and thus that, contrary to an earlier suggestion, the reaction cannot have an SN2(intermediate) mechanism. No explanation can at present be offered for the fact that methanolysis of TsiSiHPhI (like that of TsiSiMe2X with X I, OClO3, or OSO2CF3) is not accelerated by NaOMe whereas that of some other TsiSiHPhX compounds (e.g. X Br, ONO2, or OSO2Me) is so accelerated, with its implications of a duality of mechanism within an SN2 range. The reactions of the iodides TsiSiH(C6H4Y-p)I with KSCN in MeCN are also accelerated by electron withdrawal by Y, whereas those with AgOAc in MeCO2H are accelerated by electron release.
