Synthesis of a hexameric magnesium 4-pyridyl complex with cyclohexane-like ring structure via reductive C-N activation

Sam Lawrence; Matthew de Vere-Tucker; Alexandra Martha Zoya Slawin; Andreas Stasch

doi:10.3390/molecules26237214

Synthesis of a hexameric magnesium 4-pyridyl complex with cyclohexane-like ring structure via reductive C-N activation

Sam Lawrence, Matthew de Vere-Tucker, Alexandra Martha Zoya Slawin, Andreas Stasch^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

The reaction of [{(^Arnacnac)Mg}2] (^Arnacnac = HC{MeC(NAr)}₂, Ar = 2,6-diisopropylphenyl, Dip, or 2,6-diethylphenyl, Dep) with 4-dimethylaminopyridine (DMAP) at elevated temperatures af-forded the hexameric magnesium 4-pyridyl complex [{(^Arnacnac)Mg(4-C₅H₄N)}₆] via reductive cleavage of the DMAP C-N bond. The title compound contains a large s-block organometallic cyclohexane-like ring structure comprised of tetrahedral (Arnacnac)Mg nodes and linked by linear 4-pyridyl bridging ligands, and the structure is compared to other ring systems. [(^Dipnac-nac)Mg(DMAP)(NMe₂)] was structurally characterised as a by-product.

Original language	English
Article number	1471143
Number of pages	10
Journal	Molecules
Volume	26
Issue number	23
DOIs	https://doi.org/10.3390/molecules26237214
Publication status	Published - 28 Nov 2021

Keywords

Bond activation
Low oxidation state complexes
Magnesium
Metallacycles
Ring system
X-ray crystallography

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10.3390/molecules26237214Licence: CC BY

Lawrence-2021-Synthesis-of-a-hexameric-Molecules-26-07214-CCBY
Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/4.0/).
Final published version, 2.29 MBLicence: CC BY

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@article{7ba733109a38443b8223fbbe11c29453,

title = "Synthesis of a hexameric magnesium 4-pyridyl complex with cyclohexane-like ring structure via reductive C-N activation",

abstract = "The reaction of [{(Arnacnac)Mg}2] (Arnacnac = HC{MeC(NAr)}2, Ar = 2,6-diisopropylphenyl, Dip, or 2,6-diethylphenyl, Dep) with 4-dimethylaminopyridine (DMAP) at elevated temperatures af-forded the hexameric magnesium 4-pyridyl complex [{(Arnacnac)Mg(4-C5H4N)}6] via reductive cleavage of the DMAP C-N bond. The title compound contains a large s-block organometallic cyclohexane-like ring structure comprised of tetrahedral (Arnacnac)Mg nodes and linked by linear 4-pyridyl bridging ligands, and the structure is compared to other ring systems. [(Dipnac-nac)Mg(DMAP)(NMe2)] was structurally characterised as a by-product.",

keywords = "Bond activation, Low oxidation state complexes, Magnesium, Metallacycles, Ring system, X-ray crystallography",

author = "Sam Lawrence and {de Vere-Tucker}, Matthew and Slawin, {Alexandra Martha Zoya} and Andreas Stasch",

note = "The EPSRC is kindly acknowledged for research funding through a doctoral training grant (EP/N509759/1, S.R.L.) and the Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT, EP/L016419/1, M.d.V.T.). They thank the University of St Andrews for support.",

year = "2021",

month = nov,

day = "28",

doi = "10.3390/molecules26237214",

language = "English",

volume = "26",

journal = "Molecules",

issn = "1420-3049",

publisher = "Multidisciplinary Digital Publishing Institute (MDPI)",

number = "23",

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TY - JOUR

T1 - Synthesis of a hexameric magnesium 4-pyridyl complex with cyclohexane-like ring structure via reductive C-N activation

AU - Lawrence, Sam

AU - de Vere-Tucker, Matthew

AU - Slawin, Alexandra Martha Zoya

AU - Stasch, Andreas

N1 - The EPSRC is kindly acknowledged for research funding through a doctoral training grant (EP/N509759/1, S.R.L.) and the Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT, EP/L016419/1, M.d.V.T.). They thank the University of St Andrews for support.

PY - 2021/11/28

Y1 - 2021/11/28

N2 - The reaction of [{(Arnacnac)Mg}2] (Arnacnac = HC{MeC(NAr)}2, Ar = 2,6-diisopropylphenyl, Dip, or 2,6-diethylphenyl, Dep) with 4-dimethylaminopyridine (DMAP) at elevated temperatures af-forded the hexameric magnesium 4-pyridyl complex [{(Arnacnac)Mg(4-C5H4N)}6] via reductive cleavage of the DMAP C-N bond. The title compound contains a large s-block organometallic cyclohexane-like ring structure comprised of tetrahedral (Arnacnac)Mg nodes and linked by linear 4-pyridyl bridging ligands, and the structure is compared to other ring systems. [(Dipnac-nac)Mg(DMAP)(NMe2)] was structurally characterised as a by-product.

AB - The reaction of [{(Arnacnac)Mg}2] (Arnacnac = HC{MeC(NAr)}2, Ar = 2,6-diisopropylphenyl, Dip, or 2,6-diethylphenyl, Dep) with 4-dimethylaminopyridine (DMAP) at elevated temperatures af-forded the hexameric magnesium 4-pyridyl complex [{(Arnacnac)Mg(4-C5H4N)}6] via reductive cleavage of the DMAP C-N bond. The title compound contains a large s-block organometallic cyclohexane-like ring structure comprised of tetrahedral (Arnacnac)Mg nodes and linked by linear 4-pyridyl bridging ligands, and the structure is compared to other ring systems. [(Dipnac-nac)Mg(DMAP)(NMe2)] was structurally characterised as a by-product.

KW - Bond activation

KW - Low oxidation state complexes

KW - Magnesium

KW - Metallacycles

KW - Ring system

KW - X-ray crystallography

UR - https://www.mdpi.com/1420-3049/26/23/7214

U2 - 10.3390/molecules26237214

DO - 10.3390/molecules26237214

M3 - Article

SN - 1420-3049

VL - 26

JO - Molecules

JF - Molecules

IS - 23

M1 - 1471143

ER -

Synthesis of a hexameric magnesium 4-pyridyl complex with cyclohexane-like ring structure via reductive C-N activation

Abstract

Keywords

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CRITICAT CDT: Critical Resource Catalysis - CRITICAT

CCDC 2119757 - 2119759: Experimental Crystal Structure Determination

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Synthesis of a hexameric magnesium 4-pyridyl complex with cyclohexane-like ring structure via reductive C-N activation

Abstract

Keywords

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Projects

CRITICAT CDT: Critical Resource Catalysis - CRITICAT

Datasets

CCDC 2119757 - 2119759: Experimental Crystal Structure Determination

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