The reaction conditions for the synthesis [Si2(Mepz)6] (1) and [Si(Mepz)4] (4) have been investigated in detail in order to obtain suitable precursor compounds for the synthesis of the hitherto unknown Janus-head ligand tris(3,5-dimethylpyrazolyl)silanide ([Si(Mepz)3]−, MeTpsd). Within the monomeric lithium salt [Li(thf)(MeTpsd)] (5), the ambidentate silanide ligand is bound in a κ3N-fashion to the Li cation, featuring an uncoordinated, anionic silicon bridgehead. Treatment of the silanide with various electrophiles such as Me3SiCl, Me3SnCl and Ph3SnCl gave in each case the expected salt metathesis reaction with the formation of Si–Si and Si–Sn bonds, respectively. The products [Me3Si–Si(Mepz)3] (6) and [Me3Sn–Si(Mepz)3] (7) and [Ph3Sn–Si(Mepz)3] (8) are the first backbone-funtionalized derivatives originating from the tris(pyrazolyl)silanide. Overall, it could be concluded that the anionic ligand backbone of MeTpsd is much more accessible for electrophiles compared to the carbon analogue ([C(Mepz)3]−, MeTpmd).
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