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Synthesis and Characterization of Substituted Benzyl Zinc Derivatives ‐ 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
Author(s) -
Westerhausen Matthias,
Wieneke Michael,
Rademacher Bernd B.,
Schwarz Wolfgang
Publication year - 1997
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19971301024
Subject(s) - chemistry , trimethylsilyl , zinc , medicinal chemistry , lithium amide , adduct , metalation , lithium (medication) , salt metathesis reaction , amide , tetrahydrofuran , transmetalation , inorganic chemistry , metathesis , organic chemistry , catalysis , solvent , polymerization , enantioselective synthesis , medicine , polymer , endocrinology
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)LiCH(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(ZnC) bond. The extremely wide ZnNSi angle in (tmeda)Zn[CH(SiMe 3 )‐Ph[N(H)Si(SiMe 3 ) 3 of 157° is remarkable.