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Structural Effects in Lithiocuprate Chemistry: The Elucidation of Reactive Pentametallic Complexes
Author(s) -
Harford Philip J.,
Peel Andrew J.,
Taylor Joseph P.,
Komagawa Shinsuke,
Raithby Paul R.,
Robinson Thomas P.,
Uchiyama Masanobu,
Wheatley Andrew E. H.
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201304824
Subject(s) - chemistry , halide , reactivity (psychology) , structural motif , stereochemistry , medicinal chemistry , crystallography , organic chemistry , medicine , pathology , biochemistry , alternative medicine
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.