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Two-coordinate magnesium(I) dimers stabilized by super bulky amido ligands

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Date
01/08/2016
Author
Boutland, Aaron J.
Dange, Deepak
Kefalidis, Christos E.
Stasch, Andreas
Maron, Laurent
Jones, Cameron
Keywords
Bulky amides
DFT calculations
Magnesium(I)
Metal–metal bonding
QD Chemistry
NDAS
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Abstract
A variety of very bulky amido magnesium iodide complexes, LMgI(solvent)0/1 and [LMg(μ-I)(solvent)0/1]2 (L=-N(Ar)(SiR3); Ar=C6H2{C(H)Ph2}2R′-2,6,4; R=Me, Pri, Ph, or OBut; R′=Pri or Me) have been prepared by three synthetic routes. Structurally characterized examples of these materials include the first unsolvated amido magnesium halide complexes, such as [LMg(μ-I)]2 (R=Me, R′=Pri). Reductions of several such complexes with KC8 in the absence of coordinating solvents have afforded the first two-coordinate magnesium(I) dimers, LMg−MgL (R=Me, Pri or Ph; R′=Pri, or Me), in low to good yields. Reductions of two of the precursor complexes in the presence of THF have given the related THF adduct complexes, L(THF)Mg−Mg(THF)L (R=Me; R′=Pri) and LMg−Mg(THF)L (R=Pri; R′=Me) in trace yields. The X-ray crystal structures of all magnesium(I) complexes were obtained. DFT calculations on the unsolvated examples reveal their Mg−Mg bonds to be covalent and of high s-character, while Ph⋅⋅⋅Mg bonding interactions in the compounds were found to be weak at best.
Citation
Boutland , A J , Dange , D , Kefalidis , C E , Stasch , A , Maron , L & Jones , C 2016 , ' Two-coordinate magnesium(I) dimers stabilized by super bulky amido ligands ' , Angewandte Chemie International Edition , vol. 55 , no. 32 , pp. 9239–9243 . https://doi.org/10.1002/anie.201604362
Publication
Angewandte Chemie International Edition
Status
Peer reviewed
DOI
https://doi.org/10.1002/anie.201604362
ISSN
1521-3773
Type
Journal article
Rights
Copyright © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1002/anie.201604362
Description
The authors thank the Australian Research Council (C.J.), The U.S. Air Force Asian Office of Aerospace Research and Development (grant FA2386-14-1-4043 (C.J.)), and the Alexander von Humboldt Foundation for an experienced researcher grant (L.M.).
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  • University of St Andrews Research
URI
http://hdl.handle.net/10023/11007

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