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

Philip J. Harford; Andrew J. Peel; Joseph P. Taylor; Shinsuke Komagawa; P.R. Raithby; Thomas P. Robinson; Masanobu Uchiyama; Andrew E. H. Wheatley

doi:10.1002/chem.201304824

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

Philip J. Harford, Andrew J. Peel, Joseph P. Taylor, Shinsuke Komagawa, P.R. Raithby, Thomas P. Robinson, Masanobu Uchiyama, Andrew E. H. Wheatley

Department of Chemistry

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Abstract

TMPLi (TMP=2,2,6,6-tetramethylpiperidide) reacts with Cu^Isalts 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.

Original language	English
Pages (from-to)	3908-3912
Journal	Chemistry - A European Journal
Volume	20
Issue number	14
Early online date	19 Feb 2014
DOIs	https://doi.org/10.1002/chem.201304824
Publication status	Published - 1 Apr 2014

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10.1002/chem.201304824

Author's accepted version
This is the pre-peer reviewed version of the following article: Harford, P. J., Peel, A. J., Taylor, J. P., Komagawa, S., Raithby, P. R., Robinson, T. P., Uchiyama, M., & Wheatley, A. E. H. (2014). Structural effects in lithiocuprate chemistry: The elucidation of reactive pentametallic complexes. Chemistry - A European Journal., which has been published in final form at http://dx.doi.org/10.1002/chem.201304824
Accepted author manuscript, 360 KB

Cite this

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title = "Structural effects in lithiocuprate chemistry: the elucidation of reactive pentametallic complexes",

abstract = "TMPLi (TMP=2,2,6,6-tetramethylpiperidide) reacts with CuI 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.",

author = "Harford, {Philip J.} and Peel, {Andrew J.} and Taylor, {Joseph P.} and Shinsuke Komagawa and P.R. Raithby and Robinson, {Thomas P.} and Masanobu Uchiyama and Wheatley, {Andrew E. H.}",

year = "2014",

month = apr,

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doi = "10.1002/chem.201304824",

language = "English",

volume = "20",

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TY - JOUR

T1 - Structural effects in lithiocuprate chemistry

T2 - the elucidation of reactive pentametallic complexes

AU - Harford, Philip J.

AU - Peel, Andrew J.

AU - Taylor, Joseph P.

AU - Komagawa, Shinsuke

AU - Raithby, P.R.

AU - Robinson, Thomas P.

AU - Uchiyama, Masanobu

AU - Wheatley, Andrew E. H.

PY - 2014/4/1

Y1 - 2014/4/1

N2 - TMPLi (TMP=2,2,6,6-tetramethylpiperidide) reacts with CuI 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.

AB - TMPLi (TMP=2,2,6,6-tetramethylpiperidide) reacts with CuI 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.

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DO - 10.1002/chem.201304824

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JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

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ER -

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

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Time Resolved Solid State Structural Studies Across the Picosecond Time Domains

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

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Time Resolved Solid State Structural Studies Across the Picosecond Time Domains

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