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Structural effects in lithiocuprate chemistry: the elucidation of reactive pentametallic complexes.

ABSTRACT: TMPLi (TMP=2,2,6,6-tetramethylpiperidide) reacts with Cu(I) salts in the presence of Et2O to give the dimers [{(TMP)2Cu(X)Li2 (OEt2)}2] (X=CN, halide). In contrast, the use of DMPLi (DMP=cis-2,6-dimethylpiperidide) gives an unprecedented structural motif; [{(DMP)2CuLi(OEt2)}2LiX] (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.

SUBMITTER: Harford PJ 

PROVIDER: S-EPMC4497349 | biostudies-literature | 2014 Apr

REPOSITORIES: biostudies-literature

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Structural effects in lithiocuprate chemistry: the elucidation of reactive pentametallic complexes.

Harford Philip J PJ   Peel Andrew J AJ   Taylor Joseph P JP   Komagawa Shinsuke S   Raithby Paul R PR   Robinson Thomas P TP   Uchiyama Masanobu M   Wheatley Andrew E H AE  

Chemistry (Weinheim an der Bergstrasse, Germany) 20140219 14

TMPLi (TMP=2,2,6,6-tetramethylpiperidide) reacts with Cu(I) salts in the presence of Et2O to give the dimers [{(TMP)2Cu(X)Li2 (OEt2)}2] (X=CN, halide). In contrast, the use of DMPLi (DMP=cis-2,6-dimethylpiperidide) gives an unprecedented structural motif; [{(DMP)2CuLi(OEt2)}2LiX] (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. ...[more]

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