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Many Mg–Mg bonds form the core of the Mg(16)Cp*8Br(4)K cluster anion: the key to a reassessment of the Grignard reagent (GR) formation process?
It caused a sensation eight years ago, when the first room temperature stable molecular compound with a Mg–Mg bond (LMgMgL, L = chelating ligand) containing magnesium in the oxidation state +1 was prepared. Here, we report the preparation of a [Mg(16)Cp*8Br(4)K](–) cluster anion (Cp* = pentamethylcy...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Royal Society of Chemistry
2016
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5530812/ https://www.ncbi.nlm.nih.gov/pubmed/28808531 http://dx.doi.org/10.1039/c5sc03914b |
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author | Kruczyński, T. Henke, F. Neumaier, M. Bowen, K. H. Schnöckel, H. |
author_facet | Kruczyński, T. Henke, F. Neumaier, M. Bowen, K. H. Schnöckel, H. |
author_sort | Kruczyński, T. |
collection | PubMed |
description | It caused a sensation eight years ago, when the first room temperature stable molecular compound with a Mg–Mg bond (LMgMgL, L = chelating ligand) containing magnesium in the oxidation state +1 was prepared. Here, we report the preparation of a [Mg(16)Cp*8Br(4)K](–) cluster anion (Cp* = pentamethylcyclopentadiene) with 27 Mg–Mg bonds. It has been obtained through the reaction of KCp* with a metastable solution of MgBr in toluene. A highly-resolved Fourier transform mass spectrum (FT-MS) of this cluster anion, brought into vacuum by electrospraying its solution in THF, provides the title cluster's stoichiometry. This Mg(16) cluster together with experiments on the metastable solution of MgBr show that: during the formation process of GRs (Grignard reagents) which are involved in most of sophisticated syntheses of organic products, not the highly reactive MgBr radical as often presumed, but instead the metalloid Mg(16)Cp*8Br(4) cluster anion and its related cousins that are the operative intermediates along the pathway from Mg metal to GRs (e.g. Cp*MgBr). |
format | Online Article Text |
id | pubmed-5530812 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2016 |
publisher | Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-55308122017-08-14 Many Mg–Mg bonds form the core of the Mg(16)Cp*8Br(4)K cluster anion: the key to a reassessment of the Grignard reagent (GR) formation process? Kruczyński, T. Henke, F. Neumaier, M. Bowen, K. H. Schnöckel, H. Chem Sci Chemistry It caused a sensation eight years ago, when the first room temperature stable molecular compound with a Mg–Mg bond (LMgMgL, L = chelating ligand) containing magnesium in the oxidation state +1 was prepared. Here, we report the preparation of a [Mg(16)Cp*8Br(4)K](–) cluster anion (Cp* = pentamethylcyclopentadiene) with 27 Mg–Mg bonds. It has been obtained through the reaction of KCp* with a metastable solution of MgBr in toluene. A highly-resolved Fourier transform mass spectrum (FT-MS) of this cluster anion, brought into vacuum by electrospraying its solution in THF, provides the title cluster's stoichiometry. This Mg(16) cluster together with experiments on the metastable solution of MgBr show that: during the formation process of GRs (Grignard reagents) which are involved in most of sophisticated syntheses of organic products, not the highly reactive MgBr radical as often presumed, but instead the metalloid Mg(16)Cp*8Br(4) cluster anion and its related cousins that are the operative intermediates along the pathway from Mg metal to GRs (e.g. Cp*MgBr). Royal Society of Chemistry 2016-02-01 2015-11-26 /pmc/articles/PMC5530812/ /pubmed/28808531 http://dx.doi.org/10.1039/c5sc03914b Text en This journal is © The Royal Society of Chemistry 2015 http://creativecommons.org/licenses/by/3.0/ This is an Open Access article distributed under the terms of the Creative Commons Attribution 3.0 Unported License (http://creativecommons.org/licenses/by/3.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Chemistry Kruczyński, T. Henke, F. Neumaier, M. Bowen, K. H. Schnöckel, H. Many Mg–Mg bonds form the core of the Mg(16)Cp*8Br(4)K cluster anion: the key to a reassessment of the Grignard reagent (GR) formation process? |
title | Many Mg–Mg bonds form the core of the Mg(16)Cp*8Br(4)K cluster anion: the key to a reassessment of the Grignard reagent (GR) formation process?
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title_full | Many Mg–Mg bonds form the core of the Mg(16)Cp*8Br(4)K cluster anion: the key to a reassessment of the Grignard reagent (GR) formation process?
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title_fullStr | Many Mg–Mg bonds form the core of the Mg(16)Cp*8Br(4)K cluster anion: the key to a reassessment of the Grignard reagent (GR) formation process?
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title_full_unstemmed | Many Mg–Mg bonds form the core of the Mg(16)Cp*8Br(4)K cluster anion: the key to a reassessment of the Grignard reagent (GR) formation process?
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title_short | Many Mg–Mg bonds form the core of the Mg(16)Cp*8Br(4)K cluster anion: the key to a reassessment of the Grignard reagent (GR) formation process?
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title_sort | many mg–mg bonds form the core of the mg(16)cp*8br(4)k cluster anion: the key to a reassessment of the grignard reagent (gr) formation process? |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5530812/ https://www.ncbi.nlm.nih.gov/pubmed/28808531 http://dx.doi.org/10.1039/c5sc03914b |
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