Structural Effects in Lithiocuprate Chemistry: The Elucidation of Reactive Pentametallic Complexes

TMPLi (TMP=2,2,6,6-tetramethylpiperidide) reacts with Cu(I) salts in the presence of Et(2)O to give the dimers [{(TMP)(2)Cu(X)Li(2)(OEt(2))}(2)] (X=CN, halide). In contrast, the use of DMPLi (DMP=cis-2,6-dimethylpiperidide) gives an unprecedented structural motif; [{(DMP)(2)CuLi(OEt(2))}(2)LiX] (X=h...

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Detalles Bibliográficos
Autores principales: Harford, Philip J, Peel, Andrew J, Taylor, Joseph P, Komagawa, Shinsuke, Raithby, Paul R, Robinson, Thomas P, Uchiyama, Masanobu, Wheatley, Andrew E H
Formato: Online Artículo Texto
Lenguaje:English
Publicado: WILEY-VCH Verlag 2014
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4497349/
https://www.ncbi.nlm.nih.gov/pubmed/24550148
http://dx.doi.org/10.1002/chem.201304824
Descripción
Sumario:TMPLi (TMP=2,2,6,6-tetramethylpiperidide) reacts with Cu(I) salts in the presence of Et(2)O to give the dimers [{(TMP)(2)Cu(X)Li(2)(OEt(2))}(2)] (X=CN, halide). In contrast, the use of DMPLi (DMP=cis-2,6-dimethylpiperidide) gives an unprecedented structural motif; [{(DMP)(2)CuLi(OEt(2))}(2)LiX] (X=halide). This formulation suggests a hitherto unexplored route to the in situ formation of Gilman-type bases that are of proven reactivity in directed ortho cupration.

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