Two-Coordinate Magnesium(I) Dimers Stabilized by Super Bulky Amido Ligands - INSA Toulouse - Institut National des Sciences Appliquées de Toulouse Access content directly
Journal Articles Angewandte Chemie International Edition Year : 2016

Two-Coordinate Magnesium(I) Dimers Stabilized by Super Bulky Amido Ligands

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.
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Dates and versions

hal-01968739 , version 1 (03-01-2019)

Identifiers

  • HAL Id : hal-01968739 , version 1

Cite

Aaron Boutland, Deepak Dange, Andreas Stasch, Laurent Maron, Cameron Jones. Two-Coordinate Magnesium(I) Dimers Stabilized by Super Bulky Amido Ligands. Angewandte Chemie International Edition, 2016, 55 (32), pp.9239-9243. ⟨hal-01968739⟩
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