Synthesis and Characterization of Substituted Benzyl Zinc Derivatives ‐ Molecular Structures of (tmeda) Li‐CH (GeMe₃)Ph, (tmeda)Zn(CH₂Ph)₂, (tmeda)Zn[CH(SiMe₃)Ph]₂, and (tmeda)Zn[CH(SiMe₃)Ph]N(H)Si(SiMe₃)₃

Abstract

Abstract The reaction of lithium phenyl(trimethylsilyl)methanide with phenyl(trimethylsilyl)methylzinc chloride‐tmeda in the presence of tmeda yields the addition product, a bis(tmeda)‐lithium dialkylchlorozincate. The elimination of lithium chloride leads to the formation of a tmeda adduct of bis[phenyl‐(trimethylsilyl)methyl]zinc. The metathesis reaction of phenyl(trimethylsilyl)methylzinc chloride‐tmeda with lithium tris(trimethylsilyl)silylamide allows the isolation of the corresponding heteroleptic tmeda complex of an alkylzinc amide. The metalation of phenyl(trimethylstannyl)methane with butyllithium yields the transmetalation product benzyllithium. From the metathesis reaction of this lithium base with anhydrous zinc(II) chloride in the presence of tmeda, the tmeda adduct of dibenzylzinc crystallizes. The molecular structures of (tmeda)LiCH(GeMe 3 )Ph, (tmeda)Zn(CH 2 Ph) 2 , (tmeda)Zn[CH(SiMe 3 )Ph] 2 , and (tmeda)Zn[CH(SiMe 3 )‐Ph[N(H)Si(SiMe 3 ) 3 are reported. Whereas lithium bonds in an η 3 ‐fashion, the zinc atom forms a σ(ZnC) bond. The extremely wide ZnNSi angle in (tmeda)Zn[CH(SiMe 3 )‐Ph[N(H)Si(SiMe 3 ) 3 of 157° is remarkable.