Abstract
Abstract A new family of silyl complexes, (RCH2)3MSiR'3 (M = Ti, Zr), (RCH2)2Ta(=CHR)SiR'3 and (RCH2)2W(=CR)SiR'3, which are free of cyclopentadienyl (Cp) or other supporting anionic Ω-ligands, have been prepared and characterized. The silyl ligands are found to be more reactive than the alkyl ligands in the silyl alkyl and silyl alkylidene complexes. Silane (HSiR'3) elimination to form metal—carbon multiple bonds is preferred over alkane (RCH3) elimination. In the formation of (Me3SiCH2)2Ta(=CHSiMe3)Si(SiMe3)3 from the reaction of (Me3SiCH2)3TaCl2 with 2 equiv of Li(THF)3Si(SiMe3)3, an intermediate (Me3SiCH2)3Ta(Cl)Si(SiMe3)3 was identified. The first step in the conversion of this intermediate to (Me3SiCH2)2Ta(=CHSiMe3)Si(SiMe3)3 is a silane [HSi(SiMe3)3] elimination reaction to form “(Me3SiCH2)2Ta(=CHSiMe3)Cl”. The dimer of “(Me3SiCH2)2Ta(=CHSiMe3)Cl”, (Me3SiCH2)4(Cl)2Ta2(=CHSiMe3)2, was observed in the formation of (Me3SiCH2)2Ta(=CHSiMe3)Si(SiMe3)3 and in the decomposition of (Me3SiCH2)3Ta(Cl)Si(SiMe3...
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