The Reactions of the Highly Sterically Hindered Organosilicon Compound Tsisi(C₆H₄Me-P)Mei with Electrophilic Reagents and Synthesis Of Tsisii₃

Abstract

The iodide TsiSi(C₆H₄Me-p)Mel reacts with a range of silver (I) salts, AgY (Y = OCN⁻, BF₄ ⁻, OOCCF₃ ⁻, SO₄ ^2-) and mercury (II) salts, Hg₂Y(Y = OCCH₃ ⁻, SO₄ ^2-) to give the corresponding species (Me₃Si)₃ CSi(C₆Me-p)MeY and (Me₃Si)₂C(SiMe₂Y)SiMe₂(C₆H₄Me-p). The reactions with AgOCN give either the isocyanate alone or a mixture of this with the normal cyanate, depending on the reaction conditions. The reaction with AgBF₄ in Et₂O gives only TsiSi(C₆H₄Me-p)MeF while in MeOH, EtOH or i-PrOH gives the corresponding rearranged product (Me₃Si)₂C(SiMe₂Y)SiMe₂(C₆H₄Me-p) (Y=OMe⁻, OEt⁻, i-OPr). The iodide also reacts with IBr to give the rearranged bromide (Me₃Si)₂ C(SiMe₂Br)SiMe₂(C₆H₄Me-p). The highly sterically hindered triiodide, TsiSiI3 was also synthesized.

Key Words:

• Silicon
• steric hindrance
• trisyl